US5739299A - Monoazo dyes which are free from water-solubilizing groups and which contain a fluorosulphonyl group and process for colouring polyamides and polyester materials therewith - Google Patents

Monoazo dyes which are free from water-solubilizing groups and which contain a fluorosulphonyl group and process for colouring polyamides and polyester materials therewith Download PDF

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US5739299A
US5739299A US08/676,234 US67623496A US5739299A US 5739299 A US5739299 A US 5739299A US 67623496 A US67623496 A US 67623496A US 5739299 A US5739299 A US 5739299A
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Nigel Hall
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Dystar Colours Distribution GmbH
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Zeneca Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
    • D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye
    • D06P3/8233—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye using dispersed dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0014—Monoazo dyes prepared by diazotising and coupling from diazotized aminonaphthalene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0833—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5
    • C09B29/0836—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N=
    • C09B29/0838—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N= specific alkyl-CO-N-, aralkyl CON-, cycloalkyl CON-, alkyl OCON-
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/095—Amino naphthalenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C09B62/82—Azo dyes
    • C09B62/825—Monoazo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/36—Material containing ester groups using dispersed dyestuffs

Definitions

  • the present invention relates to a process for colouring synthetic textile materials, to synthetic textiles when coloured, to a process for the mass coloration of plastics, to plastics when coloured, to certain novel azo dyes and to compositions containing azo dyes.
  • GB-A-856,348 relates to water insoluble monoazo dyestuffs and discloses one specific dye containing a 4-fluorosulphonylnaphth-1-yl group which is disclaimed from the present claims.
  • GB-A-819,664 relates to water insoluble monoazo dyestuffs and discloses two specific dyes both of which are disclaimed from the present claims.
  • U.S. Pat. No. 2,576,037 relates to the coloration of cellulose acetate with certain --SO 2 F containing azo dyes.
  • Such dyes particularly those which also contain --NC 2 H 4 OH groups or derivatives thereof are dye bath unstable and as such are unsuitable for coloration of polyester textile materials.
  • a process for colouring polyamide and aromatic polyester textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1):
  • a and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one --SO 2 F group or carries a substituent to which at least one --SO 2 F group is attached except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 1-phenyl-pyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or ##STR2## or that one of A or D does not carry an --NCH 2 CH(OH)CH 2 Cl, --NCOCH 2 Cl or --NCH 2 CH 2 SO 2 F substituent.
  • Different compounds of Formula (1) may be mixed or the compounds of Formula (1) may be mixed with dyes which do not contain an --SO 2 F group.
  • the mixtures may be simple physical mixtures or may be mixed crystals formed for example by co-crystallisation. Such mixtures generally show improvement in dyeing properties. Crystalline modifications of compounds of Formula (1) exist and it is intended that the present definition includes such crystalline modifications which may be formed by heat treatment.
  • the presence of one or more --SO 2 F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet-fastness and light-fastness properties.
  • a process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A or D carries directly at least one --SO 2 F group or carries a substituent to which at least one --SO 2 F group is attached and at least one of A or D carries directly at least one ester group or carries a substituent to which at least one ester group is attached.
  • Azo dyes containing both an --SO 2 F and an ester group have improved performances in wash fastness properties over azo dyes carrying only an --SO 2 F group.
  • the synthetic textile material may be selected from secondary cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile and aromatic polyester.
  • the synthetic textile material is preferably polyamide or aromatic polyester, more preferably aromatic polyester such as polyhexamethylene adipamide or polyethylene terephthalate and especially polyethlene terephthalate.
  • Fibre blends may comprise mixtures of different synthetic textile materials or mixtures of synthetic and natural textile materials. Preferred fibre blends are those of polyester cellulose such as polyester-cotton.
  • the textile materials or blends thereof may be in the form of filaments, loose fibres, yarn, woven or knitted fibres.
  • a process for colouring a polyester textile material or fibre blend thereof which comprises applying to the polyester textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D are as herein before defined except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 1-phenylpyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or 4-nitro-2-fluorosulphonylphenyl or that one of A or D does not carry an --NCH 2 CH 2 SO 3 F substitutent.
  • a and D are as herein before defined except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optional
  • the dyes of Formula (1) preferably have low solubility in water, typically less than 1% preferably less than 0.5% and especially less than 0.2% solubility in water.
  • the dyes of Formula (1) are thus free from water solubilising groups such as --SO 3 H, --CO 3 H, --PO 3 H and quaternary amino.
  • the compounds of Formula (1) optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends thereof by methods which are conventionally employed in dyeing disperse dyes to such materials and fibre blends.
  • the process conditions may be selected from the following:
  • a migration inhibitor may optionally be added;
  • iii) printing direct at a pH of from 4 to 6.5, at a temperature of from 160° C. to 185° C. for 4 to 15 minutes for high temperature steaming, or at a temperature of from 190° C. to 225° C. for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120° C. to 140° C. and 1 to 2 bar for 10 to 45 minutes for pressure steaming, wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye may be optionally be added;
  • sequesterants may optionally be added.
  • the compound of Formula (1) is applied as a dispersion comprising from 0.001% to 4% of the compound in aqueous medium.
  • the present compounds generally provide coloured textile material which shows good fastness to washing, light and heat.
  • the heterocyclic group represented by A and D may be selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4- and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl and 1,2,4-triazolyl.
  • the carbocyclic group represented by A or D may be phenyl or naphthyl.
  • optionally substituted isoquinolinyl represented by A includes structures of the formula: ##STR3## in which m is from 1 to 4 and m is preferably 3.
  • a and D each independently is preferably thienyl, phenol, naphthyl, thiazolyl, isothiazolyl, pyridonyl, quinolinyl more preferably thien-2-yl, phenyl, naphth-1-yl, naphth-2-yl, thiazol-2-yl, isothiazol-5-yl, pyrid-4-one-5-yl or quinolinyl.
  • A is especially preferably thien-2-yl or phenyl and D is especially preferably phenyl or naphth-1-yl.
  • substituents for A and D are cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl, --OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHCOaryl, --NHSO 2 alkyl, --NHSO 2 aryl, --Salkyl, --Saryl, --SO 2 alkyl, --SO 2 aryl, --SCN or --NR 2 R 1 in which R 1 and R 2 each independently is --H, alkyl, aryl or cycloalkyl all the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R 1 and R 2 may optionally be substitute
  • each alkyl is preferably C 1-10 -alkyl
  • each alkoxy is preferably C 1-10 -alkoxy
  • each alkenyl is preferably C 2-8 -alkenyl each of which may be straight or branched chain
  • each aryl is preferably phenyl or naphthyl
  • each heterocyclic group may be any of the groups described above for A and D and each alkyl, alkoxy, alkenyl, aryl, heterocyclic or phenyl group may carry an --SO 2 F substituent.
  • R 1 and R 2 together with the --N atom to which they are attached may form a 5- or 6-membered ring such as morpolino or piperidino.
  • a further suitable substituent for A and D is a group of Formula R 19 --N--Y--X--W in which
  • Y is a direct link or C ⁇ O
  • X is a direct link, optionally substituted alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or --NR 20 --Z-- or --O--Z-- in which Z is optionally substituted alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R 20 is --H, optionally substituted alkyl, aryl or alkylaryl,
  • W is --CO 2 R 21 , --OCOR 21 , --OH or --CN in which R 21 is optionally substituted alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH,
  • R 19 is --H or optionally substituted alkyl.
  • X, Z, R 19 , R 20 or R 21 is or contains alkyl it is preferably C 1-8 -alkyl more preferably C 1-6 -alkyl each of which may be straight or branched chain or cyclic alkyl.
  • alkenyl it is preferably C 2-8 -alkenyl which may be straight or branched chain or cyclic alkenyl.
  • X, Z, R 20 or R 21 is aryl it is preferably phenyl or naphthyl more preferably phenyl.
  • X or Z is heterocyclic it may be selected from any of the heterocyclic groups defined above for A.
  • X, Z or R 21 is alkylOalkyl it is preferably C 1-6 -alkylOC 1-6 -alkyl each alkyl may be straight or branched chain and the alkylOalkyl group may be cyclic ether.
  • X or Z is alkylNHalkyl it is preferably C 1-6 -alkylNHC 1-6 -alkyl in which each alkyl may be straight or branched chain and the alkylNHalkyl group may be a cyclic amine.
  • R 20 or R 21 is alkylaryl it is preferably C 1-6 -alkylaryl more preferably C 1-6 -alkylphenyl and especially benzyl or ethylphenyl.
  • R 21 is alkylOH it is preferably C 1-6 -alkylOH.
  • the optional substituents for any of the groups represented by X, Z, R 19 , R 20 or R 21 may be selected from any of the optional substituents listed for A, D, R 1 or R 2 .
  • Preferred substituents for A and D are cyano, nitro, chloro, bromo, fluorosulphonyl, C 1-6 -alkyl, C 1-6 -alkoxy, --COC 1-6 -alkyl, --NHCOC 1-6 -alkyl, --OCOC 1-6 -alkyl, --COOC 1-6 -alkyl, phenoxy, 4--SO 2 Fphenoxy, R 19 N--Y--X--W in which R 19 , Y, X and W are as herein before defined, and --NR 1 R 2 in which R 1 and R 2 each independently is --H, C 1-6 -alkyl, C 1-6 -alkyl substituted by --OH, --CN, --Cl, phenyl, --OCOC 1-6 -alkyl, --COOC 1-6 -alkyl, ##STR5## --C 1-6 -alkyl(4-fluorosulphonylphenyl), --OCO(3-fluorosulphon
  • the compounds of Formula (1) preferably carry a total of from one to three --SO 2 F groups, more preferably one or two --SO 2 F groups and especially one --SO 2 F groups.
  • the compounds of Formula (1) more preferably carry one --SO 2 F group and one ester group.
  • a number of compounds of Formula (1) used in the above coloration process are novel and according to a further feature of the present invention there is provided a compound which is free from watersolubilising groups of Formula (2):
  • a 1 and D 1 each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A 1 or D 1 carries directly at least one --SO 2 F group or carries a substituent to which at least one --SO 2 F group is attached except for
  • a 1 is not 3,5-difluorosulphonylthien-2-yl, optionally substituted pyrazol-4-yl-5-one or N-allylpyrid-2-one-5-yl and provided that A 1 is not ##STR6## when D 1 carries an --NCH 2 CH(OH)CH 2 Cl substituent and provided than one of A 1 or D 1 is not 4-fluorosulphonylnaphth-1-yl, substituted 4-hydroxynapth-1-yl or ##STR7## and provided than A 1 is not a fluorosulphonylphenyl group when D 1 is an arylamide of an aromatic 2-hydroxycarboxylic acid.
  • a 1 and D 1 each independently may be any of the heterocyclic groups defined for A above.
  • a 1 and D 1 each independently may be any of the carbocyclic groups defined for A and D above.
  • a 1 and D 1 each independently is preferably thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl or pyridonyl, more preferably thienyl, phenyl, thiazolyl, isothiazolyl or pyridonyl and especially thien-2-yl, phenyl, thiazol-2-yl, isothiazol-5-yl or pyrid-4-one-5-yl.
  • D 1 is preferably phenyl.
  • Preferred compounds of Formulae (1) and (2) are those in which A or A 1 is phenyl and D or D 1 is phenyl; A or A 1 is thien-2-yl and D or D 1 is phenyl; and A or A 1 is phenyl and D or D 1 is naphth-1-yl.
  • a preferred sub-group of compounds of Formula (1) are those of Formula (3): ##STR8## wherein R 1 and R 2 each independently is --H or optionally substituted C 1-6 -alkyl or optionally substituted aryl;
  • R 3 , R 4 , R 5 and R 6 each independently is --H, --F, --Cl, --Br, --I, --SO 2 F or C 1-6 -alkyl, C 1-6 -alkoxy, C 1-6 -alkanoylamino, --NHSO 2 alkyl or Ophenyl each of which may be optionally substituted;
  • R 7 , R 8 and R 9 each independently is --H, C 1-6 -alkyl, --NO 2 , --COOC 1-6 -alkyl, --OCOalkyl,
  • R 7 , R 8 and R 9 is or contains alkyl the alkyl may be optionally subustituted.
  • Protected formyl groups include for example oxazolidone, imidazoline, thiazolidine, bisulphite, cyanohydrin, hydrazone and oxime.
  • the compounds of Formula (3) are novel and accordingly are a further aspect of the present invention.
  • the optional substituents for groups represented by R 1 to R 9 may be selected from any of the substituents described above for A and D.
  • the optional substituents for R 1 to R 9 are preferably --CN, --OH, --OCOC 1-6 -alkyl, --COOC 1-6 -alkyl, phenyl, --OCOphenyl, --OCOphenylSO 2 F, phenylSO 2 F, --OphenylSO 2 F, --CO 2 phenylSO 2 F, --COOC 1-6 -alkylOCOC 1-6 -alkyl and --COOC 1-6 -alkylCOOC 1-6 -alkyl.
  • Preferred compounds of Formula (3) are those in which R 1 and R 2 each independently is --CH 2 , --C 2 H 5 , --C 2 H 4 CN, --C 2 H 4 OH, --CH(CH 2 )CH 2 CH 3 , --C 4 H 9 , --CH 2 (4-fluorosulphonylphenyl), --C 2 H 4 (4-fluorosulphonylphenyl), --C 3 H 7 (4-fluorosulphonylphenyl), R 3 , R 4 , R 5 and R 6 each independently is --H, --Cl, --CH 2 , --OCH 2 , --NHCOCH 2 , --NHCOC 2 H 5 , --NHSO 2 CH 3 or --SO 2 F and R 7 , R 8 and R 9 each independently is --H, --NO 2 , --CN, --COCH 2 , --COOC 2 H 5 , --SO 2 F or --CH 3 provided that both R 7 and R 9 are not --SO 2 F.
  • Especially preferred compounds of Formula (3) are those in which
  • R 1 and R 2 each independently is --C 2 H 4 CN, --C 2 H 5 or (4-fluorosulphonylphenyl ) C 1-6 -alkyl;
  • R 3 is --H, --OCH 3 , --CH 3 or --SO 2 F;
  • R 4 and R 5 each independently is --H, --Cl or --SO 2 F;
  • R 6 is --H, --NHCOCH 3 , --NHCOC 2 H 5 , --CH 3 or --SO 2 F;
  • R 7 is --NO 2 , --COCH 3 , --COOC 2 H 5 or --SO 2 F;
  • R 8 is --H, --SO 2 F or --Cl
  • R 9 is --NO 2 , --SO 2 F or --CHO.
  • a further preferred sub-group of compounds of Formula (1) are those of Formula (4): ##STR9## wherein R 1 to R 6 are as hereinbefore defined;
  • R 10 to R 14 each independently is --H, alkoxy, alkyl, --NO 2 , --SO 2 F, --F, --Cl, --Br, --I or --CN;
  • R 10 is SO 2 F
  • R 12 is not --NO 2
  • R 11 , R 13 and R 14 are not all --H.
  • R 10 to R 14 is alkyl it is preferably C 1-10 -alkyl, more preferably C 1-6 -alkyl.
  • R 10 to R 14 is alkoxy it is preferably C 1-10 -alkoxy more preferably C 1-6 -alkoxy.
  • R 1 and R 2 each independently is --CH 3 , --C 2 H 5 , --C 3 H 7 , --C 4 H 9 , --C 5 H 11 , --C 6 H 13 , --CH(CH 3 )CH 2 CH 3 , --CH 2 phenyl, --C 2 H 4 phenyl, --C 3 H 6 phenyl, --C 2 H 4 CN, --C 2 H 4 OH, --C 2 H 4 OCH 3 , --C 2 H 4 COCH 3 , --C 4 H 8 COCH 3 , --C 2 H 4 COCH 3 , --C 2 H 4 OCOCH 3 , --C 3 H 6 OCOCH 3 , --C 4 H 8 OCOCH 3 , --C 2 H 4 OCOphenyl, --C 2 H 4 OCOphenyl (SO 2 F), --C 2 H 4 COOC 2 H 4 OCH 3 , --C 2 H 4 OC 2 H 4 COOC 2 H 4 OCH 3 , allyl
  • R 3 is --H, --OCH 3 or --Cl
  • R 4 is --H, --CH 3 , --NHCOCH 3 , --NHCOC 2 H 5 , --NHCOCH(CH 3 ) 2 , --NHCOC 3 H 6 Cl, --NHCOC(CH 3 ) 3 , --OCH 3 , --OC 4 H 9 , --F, --Cl, --Br, --I or --NHSO 2 C 1-6 -alkyl;
  • R 5 is --H , --OCH 3 , --OC 2 H 5 or --Cl;
  • R 6 is --H, --CH 3 , --OCH 3 , --F, --Cl, Br, --I or --NHSO 2 C 1-6 -alkyl;
  • R 10 is --H, --OCH 3 , --NO 2 , --Cl, --Br or --CN;
  • R 11 is --H
  • R 12 is --SO 2 F or --NO 2 ;
  • R 13 is --H, --OCH 3 , --SO 2 F, --Cl, --Br or --NO 2 ;
  • R 14 is --H, --OCH 3 , --Cl, --Br or --CN, provided that at least one of R 3 or R 5 is --H and that at least one of R 4 or R 6 is --H.
  • More preferably compounds of Formula (4) are those in which R 1 and R 2 each independently is --C 2 H 5 , --C 4 H 9 , --CH(CH 3 )CH 2 CH 3 , --C 2 H 4 OCOCH 3 , --C 4 H 8 OCOCH 3 , --C 2 H 4 OCOphenyl, --CH 2 phenyl, C 1-6 -alkylphenylSO 2 F, C 1-6 -alkylOphenylSO 2 F, ##STR11## --COOC 1-6 -alkylOCOC 1-6 -alkyl or --COOC 1-6 -alkylCOOC 1-6 -alkyl
  • R 4 is --H, --CH 3 or --NHCOCH 3 ;
  • R 3 , R 5 , R 6 and R 11 is --H
  • R 10 and R 13 each independently is --H, --Cl, --Br or --NO 2 ;
  • R 12 is --SO 2 F
  • R 14 is --H, --Cl or --Br.
  • An especially preferred compound of Formula (4) is that in which R 1 is --C 2 H 5 ; R 2 is --C 2 H 4 OCOphenyl; R 4 is --CH 3 ; R 10 and R 13 are both --Cl; R 12 is --SO 2 F; and R 3 , R 5 , R 6 , R 11 and R 14 are all --H.
  • An especially preferred sub-group of compounds of Formula (1) are those of Formula (7): ##STR12## in which R 1 and R 2 each independently is optionally substituted C 1-6 -alkyl;
  • R 4 is alkyl or a group of Formula R 19 --N--Y--X--W in which Y is a direct link or C ⁇ O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, --NR 20 --Z--, --COOZ or --O--Z in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl or a direct link and R 20 is --H, alkyl, aryl or alkylaryl, W is --CO 2 R 21 , --OCOR 21 or --OH in which R 21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R 19 is --H or alkyl;
  • R 5 is --H, C 1-6 -alkoxy or --Ophenyl
  • R 10 is --NO 2 or --Cl
  • R 13 and R 14 each independently is --H or --Cl.
  • the dyes of Formula (7) are novel and form a further feature of the present invention.
  • R 1 and R 2 each independently is preferably C 1-6 -alkyl or C 1-6 -alkyl substituted by phenyl or --COOC 1-6 -alkyl, and more preferably is ethyl, propyl, butyl, 1-methylpropyl, hexyl, benzyl, ethylphenyl or propylphenyl.
  • R 4 is preferably a group of Formula R 19 --N--Y--X--W in which
  • R 19 is preferably --H or C 1-6 -alkyl more preferably --H; Y is preferably a direct link or C ⁇ O more preferably C ⁇ O;
  • X is preferably a direct link, C 1-8 -alkyl, C 2-8 -alkenyl, any of the carbocyclic or heterocyclic groups defined above for A, C 1-6 -alkylOC 1-6 -alkyl, --NR 20 --Z--, --COOZ or --O--Z-- in which R 20 is preferably --H, C 1-6 -alkyl, phenyl or benzyl and
  • Z is preferably a direct link or C 1-6 -alkyl, C 2-8 -alkenyl, phenyl, benzyl or any of the heterocyclic groups defined above for A;
  • X is more preferably a direct link, CH 2 , C 2 H 4 , CH 2 C(CH 3 ) 2 , cyclohexyl, CH ⁇ CH, phenyl, --NR 20 --Z, --COOZ or --O--Z-- in which
  • R 20 is preferably --H, Z is preferably a direct link, C 1-6 alkyl or benzyl.
  • W is --CO 2 R 21 , --OCOR 21 or --OH in which R 21 is C 1-6 -alkyl, phenyl, chlorobenzyl, C 1-6 -alkoxybenzyl, benzyl, C 1-6 -alkylOC 1-6 -alkyl or C 1-6 -alkylOH more preferably ethyl, methyl, butyl, or 1,3-dimethylbutyl.
  • Dyes in which both A and D are phenyl and in which one of A and D carries a 4-SO 2 F group are generally more stable and build up better on polyester textile material than do the corresponding 2-SO 2 F dyes.
  • a further preferred sub-group of compounds of Formula (1) are those of Formula (5); ##STR13## wherein R 1 to R 4 and R 10 to R 14 are as herein before defined; and
  • R 15 to R 18 each independently is --H, --F, --Cl, --Br, --I, --SO 2 F, --NO 2 , --CN, --NR 1 R 2 , OH or optionally substituted --C 1-6 -alkyl or --C 1-6 -alkoxy.
  • the optional substituents for any of the groups represented by R 15 to R 18 may be selected from any of optional substituents described above for A, D, R 1 and R 2 .
  • compositions comprising dispersions of the compounds which are free from water solubilising groups of Formula (1) in which A is an optionally substituted heterocyclic or carbocyclic group; and D is an optionally substituted carbocyclic group; and at least one of A or D carries directly at least one --SO 2 F group or carried a substituent to which at least one --SO 2 F group is attached in aqueous media are novel and form a further feature of the present invention provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, 4-fluorosulphonylnaphth-1-yl, optionally substituted 1-phenylpyrazol-4-yl-5-one or ##STR14## or that one of A or D does not carry an --NCH 2 CH(OH)CH 2 Cl, --NCOCH 2 Cl or --NCH 2 CH 2 SO 2 F substituent except for
  • compositions comprising dispersions of compounds of Formulae (2), (3), (4), (5) and (7) are also novel.
  • the compositions typically comprise form 1% to 30% of a compound of Formulae (1), (2), (3), (4), (5) or (6) in an aqueous medium.
  • the compositions are preferably buffered at pH 2 to 7 more preferably at pH 4 to 6.
  • dispersions may further comprise ingredients conventionally used in dyeing applications such as dispersing agents for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or phenol/cresol/sulphanilic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl ethoxylates which may be sulphonated or phosphated, inorganic salts, de-foamers such as mineral oil or nonanol, organic liquids and buffers.
  • Dispersing agents may be present am from 10% to 200% on the weight of the compound of Formulae (1), (2), (3), (4), (5) or (7).
  • Wetting agents may be used at from 0% to 20% on the weight of the compound (1), (2), (3), (4), (5) or (7).
  • the dispersions may be prepared by bead milling the compound of Formula (1). (2), (3 , (4), (5) or (7) with glass beads or sand in an aqueous medium.
  • a process for the mass coloration of plastics which comprises incorporating into a plastics material a compound or mixture thereof which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one --SO 2 F group or carries a substituent to which at least one --SO 2 F group is attached provided that one of A or D is not 4-fluorosulphonylnaphth-1-yl, except for
  • a process for the mass coloration of plastics which comprises incorporating into a plastics material a compound or mixture thereof which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly a least one --SO 2 F group or carries a substituent to which at least one --SO 2 F group is attached and at least one of A or D carries directly at least one ester group or carries a substituent to which at least one ester group is attached.
  • the plastics may be selected from polystyrene, acrylics, styrene/acrylonitrile mixtures, acrylonitrile/butadiene/styrene mixtures, polycarbonate, polyether-sulphone, nylons, rigid PVC (uPVC) and polypropylene.
  • the compound may be incorporated by blending with granules or powdered plastics material by, for example, dry tumbling or high-speed mixing followed by injection moulding on a screw machine or by conventional compounding/masterbatching techniques.
  • the present dyes generally dissolve or disperse readily in hot plastics melt and provide bright coloration generally with good clarity and good light fastness.
  • plastics materials when coloured with the above dyes form a further feature of the present invention.
  • the compounds of Formula (1) may be obtained by usual methods for the preparation of azo compounds such as by diazotisation of an amine of Formula A--NH 2 or A 1 --NH 2 and coupling onto a component D--X or D 1 --X in which A, A 1 , D and D 1 are as hereinbefore defined and X is a group displaceable by a diazotised amine.
  • the amine, A--NH 2 or A 1 --NH 2 may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -10° C. to 10° C.
  • Coupling onto the component D--X or D 1 --X may be achieved by adding the diazotised amine to a mixture of D--X or D 1 --X in an alkanol such as methanol at a temperature from 0° C. to 10° C. After coupling the compound of Formula (1) may be recovered from the reaction mixture by any convenient means such as by filtration.
  • Fluorosulphonyl groups may be introduced into the compounds of Formula (1) or Formula (2) or into the A, A 1 , D and D 1 components prior to coupling by methods generally available in the literature.
  • reaction of the compound of Formula (1) or Formula (2), A--NH 2 , A 1 --NH 2 , the NH 2 being protected as necessary, D--X or D 1 --X, in which A, A 1 , D and D 1 are as hereinbefore defined, with chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 30° C. to 140° C. gives the chlorosulphonyl derivative.
  • the chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative.
  • the compound of Formula (1) or Formula (2), A--NH 2 , A 1 --NH 2 , D--X or D 1 --X may be sulphonated with sulphuric acid or oleum to give the sulphonic acid derivative which may be converted to the chlorosulphonyl derivative by reaction, either of the free acid or an inorganic salt thereof, with thionylchloride optionally in the presence of a chlorophosphorus compound such as phosphorus oxychloride or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 20° C. to 110° C.
  • a sulphonate ester may be converted to the corresponding chlorosulphonyl derivative.
  • the chlorosulphonyl derivative may then be converted to the fluorosulphonyl derivative as described above.
  • the compounds of Formulae (1), (2), (3), (4), (5) and (7) are useful for the coloration of synthetic textile materials particularly polyester textile materials and fibre blends thereof to which they impart colours which have excellent wet and light fastness properties.
  • the compounds of Formula (1), (2), (3), (4), (5) or (7) are also useful for the mass coloration of plastics as described above and impart bright colours generally with good clarity and light fastness.
  • 2,5-Dichloroaniline (32.4 parts) was added portionwise to chlorosulphonic acid (93 parts) at 35° C. The mixture was stirred at 120° C. for 3 hrs and then cooled to 70° C. Dimethyl formamide (1.6 parts) and thionyl chloride (15 parts) were added, maintaining the temperature at 65°-70° C. and the mixture stirred at 70° C. for 24 hours. The reaction mixture was cooled to ambient temperature and poured with caution onto stirred ice (1000 parts) producing a cream precipitate. The product was isolated by filtration, washed acid-free with ice/water and dried under vacuum to yield; 2,5-dichloro-4-chlorosulphonylaniline (44.2 parts).
  • Benzoylchloride (3.3 g) was added to a mixture of N-ethyl-N-hydroxyethyl-3-methylaniline (2.1 g) in acetone (25 cm 3 ) and pyridine (1 cm 3 ) and stirred at reflux for 1 hour. The reaction mixture was cooled and used directly in iv) below.
  • Nitrosyl sulphuric acid (3 cm 3 of 40%) was added to a mixture of 2,5-dichloro-4-fluorosulphonylaniline (2 g) in acetic/propionic acid (86:14, 25 cm 3 ) at 0° C. to 5° C.
  • the mixture was stirred at 0° C. to 5° C. for 2 hours before adding the reaction mixture from iii) above in methanol (100 cm 3 ) at 0° C. to 5° C.
  • the precipitated solid was collected by filtration, washed with water, slurried with methanol, collected by filtration and washed with methanol to give 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline (2.1 g) when applied to polyester materials from aqueous dispersion gives bluish-red shades with excellent wet and light fastness properties.
  • the dye When applied to polyester materials from an aqueous dispersion, the dye gives bright blue shades with excellent light fastness and excellent fastness to wet treatments.
  • Example 102 The dye in Example 102 (3.09 g) was stirred in DMF (30 cm 3 ) and CuCN (1.0 g) at 90° C. for 2 hours. The reaction mix was drowned onto ice and the precipitate collected, washed with water and dried under suction. The filter cake was dissolved in dichloromethane, filtered and the filtrate evaporated to give a blue dye ( ⁇ max 611 nm).
  • Example 103 The dye in Example 103 (3.09 g) was stirred in DMF (30 cm 3 ) and CuCN (1.0 g) at 90° C. for 2 hours. The reaction mix was drowned onto ice and the precipitate collected, washed with water and dried under suction. The filter cake was dissolved in dichloromethane, filtered and the filtrate evaporated to give a blue dye ( ⁇ max 608 nm).
  • Example 1 ii) The procedure of Example 1 ii) was repeated except that in place of the 32.4 parts of 2,5-dichloraniline, 32.4 parts of 2,6-dichloroaniline were used, to yield 2,6-dichloro-4-chlorosulphonylaniline (42.6 parts).
  • Example iii) The procedure of Example iii) was repeated except that in place of the 44.2 parts of 2,5-dichloro-4-chlorosulphonylaniline, 42.6 parts of 2,6-dichloro-4-chlorosulphonylaniline were used, to yield 2,6-dichloro-4-fluorosulphonylaniline (36.0 parts).
  • Example 87ii The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6-dibromo-4-fluorosulphonylaniline; 2.0 parts of 2-bromo-4-fluorosulphonylaniline were used.
  • the product, 4-(2-bromo-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (1.6 parts) ⁇ max 524 nm, when applied to polyester materials from an aqueous dispersion gives bright mid red shades with excellent fastness to light and wet treatments.
  • Example 87ii The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6-dibromo-4-fluorosulphonylaniline; 1.9 parts of 2,5-dimethoxy-4-fluorosulphonylaniline were used.
  • the product, 4-(2,5-dimethoxy-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (1.4 parts) ⁇ max 545 nm, when applied to polyester materials from an aqueous dispersion gives bluish red shades with excellent fastness to light and wet treatments.
  • Example 87ii The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6-dibromo-4-fluorosulphonylaniline; 2.0 parts of 2-nitro-5-chloro-4-fluorosulphonylaniline were used.
  • the product, 4-(2-nitro-5-chloro-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (2.6 parts) ⁇ max 550 nm, when applied to polyester materials from an aqueous dispersion gives bluish red shades with excellent fastness to light and wet treatments.
  • N-acetyl sulphanilyl chloride (100 g) was dissolved in concentrated sulphuric acid (515 cm 3 ), cooled to 4° C. and a mixture of concentrated nitric acid (38.6 cm 3 ) and concentrated sulphuric acid (42.9 cm 3 ) added dropwise maintaining the temperature at 4°-6° C. After 1 hour the reaction mix was drowned onto ice and the precipitate collected, extracted into dichloromethane and evaporated to a yellow solid (92 g). 31 g of this yellow solid was refluxed for 3 hours in water (20 cm 3 ), p-dioxane (20 cm 3 ) and KF (19.4 g) then drowned onto ice and the precipitate collected.
  • N-ethyl-N-(4-fluorosulphonylbenzyl)-3-toluidine was prepared as follows: N-Ethyl-3-toluidine (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm 3 ) and 4-fluorosulphonylbenzyl bromide (0.2 mol) were stirred at 100° C. for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (22 g). No further purification was required.
  • the 4-fluorosulphonylbenzylbromide was prepared as follows: Tosyl chloride (50 g), bromine (43 g) and carbon tetrachloride (500 mls) were stirred at reflux while shining a UV lamp (365 nm) onto the reaction. Once the solution became colourless the reaction was stopped and the solvent removed by evaporation. The resultant oil was refluxed in water (200 mls) and potassium fluoride (47 g) for three hours. After three hours the reaction mix was drowned onto ice (500 g) and the precipitate collected, washed with water and dried in vacuo. Yield 34 g of pale yellow crystals which by GLC is 54% required material, 17% starting material and 12% dibrominated species.
  • N-ethyl-N-(4-fluorosulphonylbenzyl)aniline was prepared as follows:
  • N-ethyl-N-(4-fluorosulphonylphenylpropyl)aniline was prepared as follows:
  • N-Ethylaniline (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm 3 ) and 4-fluorosulphonylphenylpropyl bromide (0.2 mol) were stirred at 100° C. for 24 hours.
  • the reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (25 g). No further purification was required.
  • the 4-fluorosulphonylphenylpropylbromide was prepared as follows:
  • Phenylpropyl bromide (19.9 g) was dissolved in chloroform (500 mls) and chlorosulphonic acid (116 g) added dropwise. Stirred for 12 hours at 40° C. then drowned onto ice (10 kg). The white precipitate was collected, redissolved in dichloromethane, washed with water, dried over magnesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 15 g. This solid was dissolved in p-dioxane (50 mls) and KF (10 g) and refluxed for three hours. After cooling to ambient the reaction mixture was drowned onto ice (400 g), extracted with dichloromethane (3 ⁇ 200 mls), dried over magnesium sulphate and evaporated to a brown oil. Yield 9 g.
  • N-(2-cyanoethyl)-N-(4-fluorosulphonylphenylethyl)aniline was prepared as follows:
  • N-(2-cyanoethyl)aniline (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm 3 ) and 4-fluorosulphonylphenylpropylbromide (0.0 mol) were stirred at 100° C. for 24 hours.
  • the reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (25 g). No further purification was required.
  • the 4-fluorosulphonylphenylpropylbromide was prepared as follows:
  • Phenylethyl bromide (36.5 g) was dissolved in chloroform (500 mls) and chlorosulphonic acid (233 g) added dropwise. Stirred for 12 hours at ambient then drowned onto ice (10kg). The white precipitate was collected, redissolved in dichloromethane, washed with water, dried over magnesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 40.8 g. This solid was dissolved in p-dioxane (200 mls) and KF (24.7 g) and refluxed for three hours. After cooling to ambient the reaction mixture was drowned onto ice (700 g), extracted with dichloromethane (3 ⁇ 200 mls), dried over magnesium sulphate and evaporated to a brown oil. Yield 33.7 g.
  • 2-Amino-3,5-dinitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm 3 ), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C.
  • the reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-ethyl-N-(4-fluorosulphonylphenylpropyl)aniline (0.01 mol), methanol (50 cm 3 ) and ice (50 g).
  • the resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C.
  • the dry dye has a ⁇ max of 617 nm and gives good fastness to washing, light and heat.
  • 2-Amino-3,5-dinitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm 3 ), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C.
  • the reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-(2-cyanoethyl), N-(4-fluorosulphonylphenylethyl) aniline (0.01 mol), methanol (50 cm 3 ) and ice (50 g).
  • the resultant precipitate was filtered, washed with water and methanol and oven dried at 50° C.
  • the dry dye has a ⁇ max of 580 nm and gives good fastness to washing, light and heat.
  • 2,4-Dinitroaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm 3 ), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C.
  • the reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N-(4-fluorosulphonylbenzyl)-N-secbutylamino)-4-methoxyacetanilide (0.01 mol), methanol (50 cm 3 ) and ice (50 g).
  • the resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C.
  • the dry dye has a ⁇ max of 575 nm and gives good fastness to washing, light and heat.
  • 2,4-Dinitro-6-bromoaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm 3 ), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C.
  • the reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N-(4-fluorosulphonylbenzyl)-N-sec butylamino)-4methoxyacetanilide (0.01 mol), methanol (50 cm 3 ) and ice (50 g).
  • the resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C.
  • the dry dye has a ⁇ max of 594 nm and gives good fastness to washing, light and heat.
  • Example 191 The dye from Example 191 (2.2 mmol) was dissolved in DMF (30 cm 3 ) and CuCN (0.2 g) and stirred at 60° C. for 1 hour. The reaction mix was drowned onto ice and the precipitate filtered. The dried filter cake was slurried in dichloromethane, filtered and the filtrate evaporated to a solid dye with ⁇ max of 642 nm.
  • Example 191 The method of Example 191 was used except that 2,4-dinitro-6-chloroaniline (0.01 mol) was used in place of the 2,4-dinitro-6-bromoaniline and 3-(N-(4-fluorosulphonylphenyl)propyl-N-n-butyl-6-methoxy)toludine (0.01 mol) was used in place of the 3-(N-(4-fluorosulphonylbenzyl)-N-secbutyl-4-methoxyacetanlide.
  • the dye has a ⁇ max of 586.5 nm and gives good fastness to washing, light and heat.
  • 2,4-Dinitroaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm 3 ), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C.
  • the reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-ethyl-N-hydroxybutyl-3-toluidine (0.01 mol), methanol (50 cm 3 ) and ice (50 g).
  • the resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C.
  • the hydroxy dye (5 mmol) was dissolved in chloroform (20 cm 3 ), potassium carbonate (0.7 g) and m-(sulphonylfluoride) benzoyl chloride (1.2 g) and refluxed for 2 hours. The reaction mix was filtered and the filtrate evaporated to yield a solid violet dye which gives good fastness to washing, light and heat.
  • 2,4-Dinitro-6-bromoaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm 3 ), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C.
  • the reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N-propyl-N-hydroxyethyl)acetanilide (0.01 mol), methanol (50 cm 3 ) and ice (50 g).
  • the resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C.
  • the hydroxy dye (5 mmol) was dissolved in chloroform (20 cm 3 ), potassium carbonate (0.7 g) and m-(sulphonylfluoride) benzoyl chloride (1.2 g) and refluxed for 2 hours. The reaction mix was filtered and the filtrate evaporated to yield a solid dye ( ⁇ max 552 nm) which gives good fastness to washing, light and heat.
  • Example 207 The procedure of Example 207 was repeated except that in place of 2 parts of N-ethyl-N-benzyl aniline; 2 parts of N,N-bis(2-acetoxyethyl)aminoacetanilide were used to yield the product, 4-(2-chloro-4-fluorosulphonylphenylazo)-3-acetamido-N,N-bis(2-acetoxyethyl)aniline (1.2 parts). When applied to polyester materials from an aqueous dispersion, the dye gave orange shades. ⁇ max 494 nm.
  • the damp solid was slurried in water and re-filtered.
  • the dye was then stirred in methanol at room temperature for 1 hour, filtered, and dried at 50° C. to yield the product, 4-(2-methoxy-5-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-benzyl aniline (1.5 parts).
  • the dye When applied to polyester materials from an aqueous dispersion, the dye gave yellow shades. ⁇ max 450.
  • Example 220iv The procedure of Example 220iv) was repeated except that in place of the 3-N,N-diethylaminoacetanilide 0.4 parts of 3-methyl-N,N-diethylaminoaniline was used to yield 4-(3-nitro-5-fluorosulphonylthien-2ylazo)-3-methyl-N,N-diethylaminoaniline (0.3 parts).
  • the dye When applied to polyester materials from an aqueous dispersion the dye gave blue shades. ⁇ max 629 nm.
  • N-acetyl sulphanilyl chloride (100 g) was dissolved in concentrated sulphuric acid (515 cm 3 ), cooled to 4° C. and a mixture of concentrated nitric acid (38.6 cm 3 ) and concentrated sulphuric acid (42.9 cm 3 ) added dropwise maintaining the temperature at 4°-6° C. After hour the reaction mix was drowned onto ice and the precipitate collected, extracted into dichloromethane and evaporated to a yellow solid (92 g). 31 g of this yellow solid was refluxed for 3 hours in water (20 cm 3 ), p-dioxane (20 cm 3 ) and KF (19.4 g). then drowned onto ice and the precipitate collected.
  • Dye Examples 222-224, 226, 229 and 231-235 were prepared from the appropriate N,N-dialkyl-(3-ethylsuccinamido-6-methoxy)aniline coupling components which were prepared according to the following method.
  • a mixture of 3-(N,N-dialkyl)-4-methoxyaniline (0.01 mol), ethylsuccinyl chloride (0.01 mol) and pyridine (0.01 mol) in dichloromethane (50 ml) was stirred and heated under gentle reflux for 4 h and then allowed to cool and was then drowned out into water.
  • the resulting product was extracted into dichloromethane, dried (MgSO 4 ) and evaporated to dryness in vacuo to yield the required Coupler as a brown oil.
  • Dye Examples 225, 227, 228, 230 and 236-238 were prepared from the appropriate N,N-dialkyl-(3-ethylsuccinamido-6-methoxy)aniline coupling components which were prepared according to the following method.
  • a mixture of 3-(N,N-dialkylamino)-4-methoxyaniline (0.01 mol) and succinic anhydride (0.01 mol) in anhydrous toluene (50 ml) was stirred for 1.5 h and then evaporated to dryness in vacuo to give a brown gum.
  • the brown gum (the carboxylic acid intermediate) was esterified by treatment with an appropriate alcohol (0.1 mol) and conc. sulphuric acid (1 ml) at 100° C.
  • Dye Examples 239-246 were prepared using the same general method as was used for the preparation of dye examples 222-238.
  • the dyes when applied to polyester as aqueous dispersions, gave good fastness to washing light and heat.
  • the couplers for dye Examples 239, 240 and 246 were prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method using acetylsalicoyl chloride (0.01 mol) in place of ethylsuccinyl chloride.
  • the coupler for dye Example 241 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using butylchloroformate (0.01 mol) in place of ethylsuccinyl chloride.
  • the coupler for dye Example 242 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using ethylmalonyl chloride (0.01 mol) in place of ethylsuccinyl chloride.
  • the coupler for dye Example 243 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 2 using maleic anhydride (0.01 mol) in place of succinic anhydride and ethanol as the esterifying alcohol.
  • the coupler for dye Example 244 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 2 using 2,2-dimethylsuccinic anhydride (0.01 mol) in place of succinic anhydride and ethanol as the esterifying alcohol.
  • the coupler for dye Example 245 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using 4-methoxycarbonylphenylchloroformate (0.01 mol) in place of ethylsuccinyl chloride.
  • Example 1 The procedure of Example 1 was repeated except that in place of the 1.6 parts of N,N-bis-(2-cyanoethyl)aniline; 1.5 parts of 4,6-diamino-2-propylthiopyrimidine were used.
  • the product, 5-(2,5-dichloro-4-fluorosulphonylphenylazo)-4,6-diaminopropylthiopyrimidine (3.4 parts) ⁇ max 420 nm, when applied to polyester materials from an aqueous dispersion gives bright yellow shades with excellent fastness to light and wet treatments.
  • Example 1 The procedure of Example 1 was repeated except that in place of the 1.6 parts of N,N-bis-(2-cyanoethyl)aniline; 2.6 parts of 3-chloro-N-ethyl,N-methylphthalimidoaniline were used.
  • the product, 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-chloro-N-ethyl, N-methylphthalimidoaniline (4.0 parts) ⁇ max 455 nm, when applied to polyester materials from an aqueous dispersion gives orange shades with excellent fastness to light and wet treatments.
  • Example 2 The procedure of Example 1 was repeated except that in place of the 1.6 parts of N,N-bis-(2-cyanoethyl)aniline; 1.5 parts of 3-methylmorpholinobenzene were used.
  • the product, 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methylmorpholinobenzene (1.9 parts) ⁇ max 480 nm, when applied to polyester materials from an aqueous dispersion gives dull bluish red shades with excellent fastness to light and wet treatments.
  • Example 139 The procedure of Example 139 was used expect that 1-(N-ethylamino)naphthalene (7.86 nmol) was used in place of the 3-(N,N-diethylamino)acetanilide.
  • the dye has a ⁇ max of 571 nm.
  • Example 139 The procedure of Example 139 was used except that 1-(N-ethyl-N-n-proylamino)naphthalene was used in place of the 3-(N,N-diethylamino)acetanilide.
  • the dye has a ⁇ max of 578 nm.
  • the diazo solution was added to a mixture of N,N-diethylaniline (0.9 parts), methanol (50 parts) and sulphamic acid (0.5 parts); stirring at 0.5° C. After stirring for 2 hours at this temperature, the product was isolated by filtration, washed with water and dried at 50° C. to yield; 4-(4,8-difluorosulphonylnaphthyl-2-azo)-N,N-diethylaniline (1.6 parts).
  • the dye gives red shades with excellent fastness to wet treatments. ⁇ max of 500 nm.
  • the diazo solution was added to a mixture of N-ethyl,N-2-(4-fluorosulphonylphenoxyl)-ethylaniline (3.0 parts), methanol (50 parts) and sulphamic acid (0.5 parts); stirring at 0.5° C. After stirring for 2 hours at this temperature, the product was isolated by filtration, washed with water and dried at 50° C. to yield; 4-(2-cyano-4-nitrophenylazo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (3.0 parts).
  • the dye gives bluish red shades with excellent light fastness and excellent fastness to wet treatments. ⁇ max of 530 nm.
  • Example 257 The procedure of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.7 parts of 2-amino-3-acetyl-5-notrothiophene were used.
  • the filter cake was set stirring with 1,4-dioxan (40 parts) and a solution of potassium fluoride (1.8 parts) in water (1.0 parts) was added. The mixture was heated at 60° C. for 3 hours, cooled to ambient and the product was isolated by filtration to yield; 3-methyl-4-(2-chloro-4-nitrophenylazo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (4.5 parts).
  • Example 257 The procedure of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.9 parts of 2-amino-6-thiocyanatobenzthiazole were used.
  • Example 257 The procedure of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.9 parts of 2-amino-6-thiocyanatobenzthiazole were used.
  • Example 257 The procedure of Example 257 was repeated except that in place of the 3.0 parts of N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline, 3.1 parts of N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethyl-m-toluidine were used.
  • Dyes prepared by the procedure described for Example 139 but using the 1-naphthylamino in place of 3-(N,N-diethylamino)acetanilide are of Formula:
  • Example 1 The procedure of Example 1 was repeated except that in place of the 3.0 g of 3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline., 1.8 g of 1-n-butyl-3-cyano-6-hydroxy-4-methyl-2-oxo-IH-pyridine were used.
  • Example 1 The procedure of Example 1 was repeated except that in place of the 3.0 g of 3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline,. 1.5 g of 1-phenyl-3-t-butyl-5-aminopyrazole were used.
  • the product 1-phenyl-3-t-butyl-5-amino-4-(2,5-dichloro-4-fluorosulphonylphenylazo)pyrazole (2.1 g) when applied to polyester materials form aqueous dispersion gives greenish yellow shades with excellent wet and light fastness properties. ⁇ max 442 nm.
  • the dyes of the following formulae may be made by the procedure of Example 1 by diazotising the appropriate amino and coupling onto the appropriate coupling component

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  • Textile Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
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  • Quinoline Compounds (AREA)

Abstract

A process for coloring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilizing groups, of Formula (1):
A--N═N--D                                              Formula (1)
wherein
A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 1-phenyl-pyrazol-4-yl-5-one or ##STR1## or that one of A or D does not carry an --NCH2 CH(OH)CH2 Cl, --NCOCH2 Cl or --NCH2 CH2 SO2 F substituent.
The presence of one or more --SO2 F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet fastness and light fastness properties.

Description

This application claims benefit of international application PCT/GB94/02831, filed Dec. 30, 1994.
The present invention relates to a process for colouring synthetic textile materials, to synthetic textiles when coloured, to a process for the mass coloration of plastics, to plastics when coloured, to certain novel azo dyes and to compositions containing azo dyes.
GB-A-856,348 relates to water insoluble monoazo dyestuffs and discloses one specific dye containing a 4-fluorosulphonylnaphth-1-yl group which is disclaimed from the present claims.
GB-A-819,664 relates to water insoluble monoazo dyestuffs and discloses two specific dyes both of which are disclaimed from the present claims.
U.S. Pat. No. 2,576,037 relates to the coloration of cellulose acetate with certain --SO2 F containing azo dyes. Such dyes, particularly those which also contain --NC2 H4 OH groups or derivatives thereof are dye bath unstable and as such are unsuitable for coloration of polyester textile materials.
According to the present invention there is provided a process for colouring polyamide and aromatic polyester textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1):
A--N═N--D                                              Formula (1)
wherein
A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 1-phenyl-pyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or ##STR2## or that one of A or D does not carry an --NCH2 CH(OH)CH2 Cl, --NCOCH2 Cl or --NCH2 CH2 SO2 F substituent.
Different compounds of Formula (1) may be mixed or the compounds of Formula (1) may be mixed with dyes which do not contain an --SO2 F group. The mixtures may be simple physical mixtures or may be mixed crystals formed for example by co-crystallisation. Such mixtures generally show improvement in dyeing properties. Crystalline modifications of compounds of Formula (1) exist and it is intended that the present definition includes such crystalline modifications which may be formed by heat treatment.
The presence of one or more --SO2 F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet-fastness and light-fastness properties.
According to a first embodiment of the present invention there is provided a process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A or D carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached and at least one of A or D carries directly at least one ester group or carries a substituent to which at least one ester group is attached.
Azo dyes containing both an --SO2 F and an ester group have improved performances in wash fastness properties over azo dyes carrying only an --SO2 F group.
The synthetic textile material may be selected from secondary cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile and aromatic polyester. The synthetic textile material is preferably polyamide or aromatic polyester, more preferably aromatic polyester such as polyhexamethylene adipamide or polyethylene terephthalate and especially polyethlene terephthalate. Fibre blends may comprise mixtures of different synthetic textile materials or mixtures of synthetic and natural textile materials. Preferred fibre blends are those of polyester cellulose such as polyester-cotton. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn, woven or knitted fibres.
According to a second embodiment of the present invention there is provided a process for colouring a polyester textile material or fibre blend thereof which comprises applying to the polyester textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D are as herein before defined except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted 1-phenylpyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or 4-nitro-2-fluorosulphonylphenyl or that one of A or D does not carry an --NCH2 CH2 SO3 F substitutent.
The dyes of Formula (1) preferably have low solubility in water, typically less than 1% preferably less than 0.5% and especially less than 0.2% solubility in water. The dyes of Formula (1) are thus free from water solubilising groups such as --SO3 H, --CO3 H, --PO3 H and quaternary amino.
The compounds of Formula (1), optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends thereof by methods which are conventionally employed in dyeing disperse dyes to such materials and fibre blends.
The process conditions may be selected from the following:
i) exhaust dyeing at a pH of from 4 to 6.5, an a temperature of from 125° C. to 140° C. for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, a sequestrant may be optionally be added;
ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 190° C. to 225° C. for from 15 seconds to 5 minutes, a migration inhibitor may optionally be added;
iii) printing direct at a pH of from 4 to 6.5, at a temperature of from 160° C. to 185° C. for 4 to 15 minutes for high temperature steaming, or at a temperature of from 190° C. to 225° C. for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120° C. to 140° C. and 1 to 2 bar for 10 to 45 minutes for pressure steaming, wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye may be optionally be added;
iv) discharge printing (by padding the dye onto the textile material, drying and overprinting) at a pH of from 4 to 6.5, migration inhibitors and thickeners may optionally be added;
v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 95° C. to 100° C. using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, sequesterants may optionally be added; and
vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 85° C. for acetate or at a temperature of 90° C. for triacetate and nylon for from 15 to 90 minutes, sequesterants may optionally be added.
In all the above processes the compound of Formula (1) is applied as a dispersion comprising from 0.001% to 4% of the compound in aqueous medium.
The present compounds generally provide coloured textile material which shows good fastness to washing, light and heat.
The heterocyclic group represented by A and D may be selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4- and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl and 1,2,4-triazolyl. The carbocyclic group represented by A or D may be phenyl or naphthyl.
For the avoidance of doubt optionally substituted isoquinolinyl represented by A includes structures of the formula: ##STR3## in which m is from 1 to 4 and m is preferably 3.
A and D each independently is preferably thienyl, phenol, naphthyl, thiazolyl, isothiazolyl, pyridonyl, quinolinyl more preferably thien-2-yl, phenyl, naphth-1-yl, naphth-2-yl, thiazol-2-yl, isothiazol-5-yl, pyrid-4-one-5-yl or quinolinyl. A is especially preferably thien-2-yl or phenyl and D is especially preferably phenyl or naphth-1-yl.
Examples of suitable substituents for A and D are cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl, --OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHCOaryl, --NHSO2 alkyl, --NHSO2 aryl, --Salkyl, --Saryl, --SO2 alkyl, --SO2 aryl, --SCN or --NR2 R1 in which R1 and R2 each independently is --H, alkyl, aryl or cycloalkyl all the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 may optionally be substituted by --OH, --CN, --F, --Cl, --Br, --I, --SO2 F, alkoxy, alkenyl, phenyl, phenylSO2 F, aryloxy, aryloxySO2 F, --N(alkyl)2, --OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, --COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO2 F, --OCOphenylNO2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, --OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkylOalkyl, --COOalkylOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, --OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, --OalkylCOOalkylCOOalkyl, --OalkylOCOalkylOalkyl, --COOalkylOCOalkyl or --COOalkylCOOalkyl, ##STR4## in which L is --H or alkyl.
In all of the suitable substitutents for A and D each alkyl is preferably C1-10 -alkyl, each alkoxy is preferably C1-10 -alkoxy, each alkenyl is preferably C2-8 -alkenyl each of which may be straight or branched chain, each aryl is preferably phenyl or naphthyl and each heterocyclic group may be any of the groups described above for A and D and each alkyl, alkoxy, alkenyl, aryl, heterocyclic or phenyl group may carry an --SO2 F substituent. R1 and R2 together with the --N atom to which they are attached may form a 5- or 6-membered ring such as morpolino or piperidino.
A further suitable substituent for A and D is a group of Formula R19 --N--Y--X--W in which
Y is a direct link or C═O,
X is a direct link, optionally substituted alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or --NR20 --Z-- or --O--Z-- in which Z is optionally substituted alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R20 is --H, optionally substituted alkyl, aryl or alkylaryl,
W is --CO2 R21, --OCOR21, --OH or --CN in which R21 is optionally substituted alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH,
R19 is --H or optionally substituted alkyl.
Where X, Z, R19, R20 or R21 is or contains alkyl it is preferably C1-8 -alkyl more preferably C1-6 -alkyl each of which may be straight or branched chain or cyclic alkyl. Where X or Z is alkenyl it is preferably C2-8 -alkenyl which may be straight or branched chain or cyclic alkenyl. Where X, Z, R20 or R21 is aryl it is preferably phenyl or naphthyl more preferably phenyl. Where X or Z is heterocyclic it may be selected from any of the heterocyclic groups defined above for A. Where X, Z or R21 is alkylOalkyl it is preferably C1-6 -alkylOC1-6 -alkyl each alkyl may be straight or branched chain and the alkylOalkyl group may be cyclic ether. Where X or Z is alkylNHalkyl it is preferably C1-6 -alkylNHC1-6 -alkyl in which each alkyl may be straight or branched chain and the alkylNHalkyl group may be a cyclic amine. Where R20 or R21 is alkylaryl it is preferably C1-6 -alkylaryl more preferably C1-6 -alkylphenyl and especially benzyl or ethylphenyl. Where R21 is alkylOH it is preferably C1-6 -alkylOH.
The optional substituents for any of the groups represented by X, Z, R19, R20 or R21 may be selected from any of the optional substituents listed for A, D, R1 or R2.
Preferred substituents for A and D are cyano, nitro, chloro, bromo, fluorosulphonyl, C1-6 -alkyl, C1-6 -alkoxy, --COC1-6 -alkyl, --NHCOC1-6 -alkyl, --OCOC1-6 -alkyl, --COOC1-6 -alkyl, phenoxy, 4--SO2 Fphenoxy, R19 N--Y--X--W in which R19, Y, X and W are as herein before defined, and --NR1 R2 in which R1 and R2 each independently is --H, C1-6 -alkyl, C1-6 -alkyl substituted by --OH, --CN, --Cl, phenyl, --OCOC1-6 -alkyl, --COOC1-6 -alkyl, ##STR5## --C1-6 -alkyl(4-fluorosulphonylphenyl), --OCO(3-fluorosulphonylphenyl), --OCO(4-fluorosulphonylphenyl), --C2-4 -alkenyl, --COOC1-6 -alkylOC1-6 -alkyl, --OC1-6 -alkylCN, --OC1-6 -alkylOCOC1-6 -alkylOC1-6 -alkyl, --COOalkylOCOalkyl and --COOalkylCOOalkyl or where R1 and R2 together with the --N atom to which they are attached form a morpholino or piperidino ring.
The compounds of Formula (1) preferably carry a total of from one to three --SO2 F groups, more preferably one or two --SO2 F groups and especially one --SO2 F groups.
The compounds of Formula (1) more preferably carry one --SO2 F group and one ester group.
A number of compounds of Formula (1) used in the above coloration process are novel and according to a further feature of the present invention there is provided a compound which is free from watersolubilising groups of Formula (2):
A.sup.1 --N═N--D.sup.1                                 Formula ( 2)
in which:
A1 and D1 each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A1 or D1 carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached except for
4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline,
4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline,
4-(4-fluorosulphonylphenylazo)-N-ethyl-N-acetoxyethylaniline,
1-(5-fluorosulphonyl-2-methylphenylazo)-2-hydroxynaphthalene,
4-(4-fluorosulphonylphenylazo)-3-(trifluoromethylcarbonylamino)-N-ethyl-N-2-methoxyethyl)aniline,
4-(4-fluorosulphonylphenylazo)-3-(trifluoromethylcarbonylamino)-N-ethyl-N-2-cyanoethyl)aniline,
4-(4-fluorosulphonylphenylazo)-2,5-dimethyl-N-ethyl-N-(2-methoxyethyl)aniline,
4-(4-fluorosulphonylphenylazo)-2,5-dimethyl-N-ethyl-N-(2-cyanoethyl)aniline
4-(4-fluorosulphonylphenylazo)-N-ethyl-N-(2-fluorosulphonylethyl)aniline,
4-(4-fluorosulphonylphenylazo)-N,N-di(2-fluorosulphonylethyl)aniline,
4-(3-fluorosulphonyl-4-methylphenylazo)-3-(trifluoromethylcarbonylamino)-N-ethyl-N-(2-methoxyethyl)aniline,
4-(3-fluorosulphonyl-4-methylphenylazo)-2,5-dimethyl-N-ethyl-N-(2-methoxyethyl)aniline,
4-(3-fluorosulphonyl-4-chlorophenylazo)-3-(trifluoromethylcarbonylamino)-N-ethyl-N-(2-methoxyethyl)aniline,
4-(3-fluorosulphonyl-4-chlorophenylazo)-2,5-dimethyl-N-ethyl-N-(2-methoxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-1-aminonaphthalene,
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline,
4-(3-fluorosulphonylphenylazo)-2,5-dimethoxyaniline,
4-(2-chloro-4-nitrophenylazo)-2-methyl-5-fluorosulphonylaniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N-(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-diethylaniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline,
4-(5-fluorosulphonyl-2-chlorophenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(3-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline,
4-(4-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N-ethyl-N-(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-chlorophenylazo)-N-ethyl--N(((2-methoxy)-2-ethoxy)ethyl)aniline, 4-(3-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N-ethyl-N((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazonaphth-1-ylamine,
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline,
4-(3-fluorosulphonyl(phenylazo)-3,6-dimethoxyaniline, provided that A1 is not 3,5-difluorosulphonylthien-2-yl, optionally substituted pyrazol-4-yl-5-one or N-allylpyrid-2-one-5-yl and provided that A1 is not ##STR6## when D1 carries an --NCH2 CH(OH)CH2 Cl substituent and provided than one of A1 or D1 is not 4-fluorosulphonylnaphth-1-yl, substituted 4-hydroxynapth-1-yl or ##STR7## and provided than A1 is not a fluorosulphonylphenyl group when D1 is an arylamide of an aromatic 2-hydroxycarboxylic acid.
A1 and D1 each independently may be any of the heterocyclic groups defined for A above. A1 and D1 each independently may be any of the carbocyclic groups defined for A and D above.
A1 and D1 each independently is preferably thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl or pyridonyl, more preferably thienyl, phenyl, thiazolyl, isothiazolyl or pyridonyl and especially thien-2-yl, phenyl, thiazol-2-yl, isothiazol-5-yl or pyrid-4-one-5-yl.
D1 is preferably phenyl.
Preferred compounds of Formulae (1) and (2) are those in which A or A1 is phenyl and D or D1 is phenyl; A or A1 is thien-2-yl and D or D1 is phenyl; and A or A1 is phenyl and D or D1 is naphth-1-yl.
The optional substituents for A1 and D1 are any of those defined for A and D above.
A preferred sub-group of compounds of Formula (1) are those of Formula (3): ##STR8## wherein R1 and R2 each independently is --H or optionally substituted C1-6 -alkyl or optionally substituted aryl;
R3, R4, R5 and R6 each independently is --H, --F, --Cl, --Br, --I, --SO2 F or C1-6 -alkyl, C1-6 -alkoxy, C1-6 -alkanoylamino, --NHSO2 alkyl or Ophenyl each of which may be optionally substituted;
R7, R8 and R9 each independently is --H, C1-6 -alkyl, --NO2, --COOC1-6 -alkyl, --OCOalkyl,
--Cl, --F, --Br, --I, --COC1-6 -alkyl, --CN, formyl, protected formyl or --SO2 F provided that at least one of R1 to R9 is --SO2 F or carries a substituent to which at least one --SO2 F group is attached and provided that R7 and R9 are not both
--SO2 F.
Where R7, R8 and R9 is or contains alkyl the alkyl may be optionally subustituted.
Protected formyl groups include for example oxazolidone, imidazoline, thiazolidine, bisulphite, cyanohydrin, hydrazone and oxime.
The compounds of Formula (3) are novel and accordingly are a further aspect of the present invention.
The optional substituents for groups represented by R1 to R9 may be selected from any of the substituents described above for A and D. The optional substituents for R1 to R9 are preferably --CN, --OH, --OCOC1-6 -alkyl, --COOC1-6 -alkyl, phenyl, --OCOphenyl, --OCOphenylSO2 F, phenylSO2 F, --OphenylSO2 F, --CO2 phenylSO2 F, --COOC1-6 -alkylOCOC1-6 -alkyl and --COOC1-6 -alkylCOOC1-6 -alkyl.
Preferred compounds of Formula (3) are those in which R1 and R2 each independently is --CH2, --C2 H5, --C2 H4 CN, --C2 H4 OH, --CH(CH2)CH2 CH3, --C4 H9, --CH2 (4-fluorosulphonylphenyl), --C2 H4 (4-fluorosulphonylphenyl), --C3 H7 (4-fluorosulphonylphenyl), R3, R4, R5 and R6 each independently is --H, --Cl, --CH2, --OCH2, --NHCOCH2, --NHCOC2 H5, --NHSO2 CH3 or --SO2 F and R7, R8 and R9 each independently is --H, --NO2, --CN, --COCH2, --COOC2 H5, --SO2 F or --CH3 provided that both R7 and R9 are not --SO2 F.
Especially preferred compounds of Formula (3) are those in which
R1 and R2 each independently is --C2 H4 CN, --C2 H5 or (4-fluorosulphonylphenyl ) C1-6 -alkyl;
R3 is --H, --OCH3, --CH3 or --SO2 F;
R4 and R5 each independently is --H, --Cl or --SO2 F;
R6 is --H, --NHCOCH3, --NHCOC2 H5, --CH3 or --SO2 F;
R7 is --NO2, --COCH3, --COOC2 H5 or --SO2 F;
R8 is --H, --SO2 F or --Cl;
R9 is --NO2, --SO2 F or --CHO.
A further preferred sub-group of compounds of Formula (1) are those of Formula (4): ##STR9## wherein R1 to R6 are as hereinbefore defined;
R10 to R14 each independently is --H, alkoxy, alkyl, --NO2, --SO2 F, --F, --Cl, --Br, --I or --CN;
provided that when R10 is SO2 F, R12 is not --NO2 and R11, R13 and R14 are not all --H.
Where a group represented by R10 to R14 is alkyl it is preferably C1-10 -alkyl, more preferably C1-6 -alkyl. Where a group represented by R10 to R14 is alkoxy it is preferably C1-10 -alkoxy more preferably C1-6 -alkoxy.
Compounds of Formula (4) are preferably those in which R1 and R2 each independently is --CH3, --C2 H5, --C3 H7, --C4 H9, --C5 H11, --C6 H13, --CH(CH3)CH2 CH3, --CH2 phenyl, --C2 H4 phenyl, --C3 H6 phenyl, --C2 H4 CN, --C2 H4 OH, --C2 H4 OCH3, --C2 H4 COCH3, --C4 H8 COCH3, --C2 H4 COCH3, --C2 H4 OCOCH3, --C3 H6 OCOCH3, --C4 H8 OCOCH3, --C2 H4 OCOphenyl, --C2 H4 OCOphenyl (SO2 F), --C2 H4 COOC2 H4 OCH3, --C2 H4 OC2 H4 COOC2 H4 OCH3, allyl, --C2 H4 Ophenyl, --C2 H4 O(fluorosulphonylphenyl), --CH2 CH(CN) (OC2 H4), C1-6 -alkylphenylSO2 F, ##STR10## --COOC1-6 -alkylOCOC1-6 -alkyl or --COOC1-6 -alkyl COOC1-6 -alkyl
R3 is --H, --OCH3 or --Cl;
R4 is --H, --CH3, --NHCOCH3, --NHCOC2 H5, --NHCOCH(CH3)2, --NHCOC3 H6 Cl, --NHCOC(CH3)3, --OCH3, --OC4 H9, --F, --Cl, --Br, --I or --NHSO2 C1-6 -alkyl;
R5 is --H , --OCH3, --OC2 H5 or --Cl;
R6 is --H, --CH3, --OCH3, --F, --Cl, Br, --I or --NHSO2 C1-6 -alkyl;
R10 is --H, --OCH3, --NO2, --Cl, --Br or --CN;
R11 is --H;
R12 is --SO2 F or --NO2 ;
R13 is --H, --OCH3, --SO2 F, --Cl, --Br or --NO2 ; and
R14 is --H, --OCH3, --Cl, --Br or --CN, provided that at least one of R3 or R5 is --H and that at least one of R4 or R6 is --H.
More preferably compounds of Formula (4) are those in which R1 and R2 each independently is --C2 H5, --C4 H9, --CH(CH3)CH2 CH3, --C2 H4 OCOCH3, --C4 H8 OCOCH3, --C2 H4 OCOphenyl, --CH2 phenyl, C1-6 -alkylphenylSO2 F, C1-6 -alkylOphenylSO2 F, ##STR11## --COOC1-6 -alkylOCOC1-6 -alkyl or --COOC1-6 -alkylCOOC1-6 -alkyl
R4 is --H, --CH3 or --NHCOCH3 ;
R3, R5, R6 and R11 is --H;
R10 and R13 each independently is --H, --Cl, --Br or --NO2 ;
R12 is --SO2 F; and
R14 is --H, --Cl or --Br.
An especially preferred compound of Formula (4) is that in which R1 is --C2 H5 ; R2 is --C2 H4 OCOphenyl; R4 is --CH3 ; R10 and R13 are both --Cl; R12 is --SO2 F; and R3, R5, R6, R11 and R14 are all --H.
An especially preferred sub-group of compounds of Formula (1) are those of Formula (7): ##STR12## in which R1 and R2 each independently is optionally substituted C1-6 -alkyl;
R4 is alkyl or a group of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, --NR20 --Z--, --COOZ or --O--Z in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl or a direct link and R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCOR21 or --OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or alkyl;
R5 is --H, C1-6 -alkoxy or --Ophenyl;
R10 is --NO2 or --Cl; and
R13 and R14 each independently is --H or --Cl.
The dyes of Formula (7) are novel and form a further feature of the present invention.
In the dyes of Formula (7)
R1 and R2 each independently is preferably C1-6 -alkyl or C1-6 -alkyl substituted by phenyl or --COOC1-6 -alkyl, and more preferably is ethyl, propyl, butyl, 1-methylpropyl, hexyl, benzyl, ethylphenyl or propylphenyl.
R4 is preferably a group of Formula R19 --N--Y--X--W in which
R19 is preferably --H or C1-6 -alkyl more preferably --H; Y is preferably a direct link or C═O more preferably C═O;
X is preferably a direct link, C1-8 -alkyl, C2-8 -alkenyl, any of the carbocyclic or heterocyclic groups defined above for A, C1-6 -alkylOC1-6 -alkyl, --NR20 --Z--, --COOZ or --O--Z-- in which R20 is preferably --H, C1-6 -alkyl, phenyl or benzyl and
Z is preferably a direct link or C1-6 -alkyl, C2-8 -alkenyl, phenyl, benzyl or any of the heterocyclic groups defined above for A;
X is more preferably a direct link, CH2, C2 H4, CH2 C(CH3)2, cyclohexyl, CH═CH, phenyl, --NR20 --Z, --COOZ or --O--Z-- in which
R20 is preferably --H, Z is preferably a direct link, C1-6 alkyl or benzyl.
W is --CO2 R 21, --OCOR21 or --OH in which R21 is C1-6 -alkyl, phenyl, chlorobenzyl, C1-6 -alkoxybenzyl, benzyl, C1-6 -alkylOC1-6 -alkyl or C1-6 -alkylOH more preferably ethyl, methyl, butyl, or 1,3-dimethylbutyl.
Dyes in which both A and D are phenyl and in which one of A and D carries a 4-SO2 F group are generally more stable and build up better on polyester textile material than do the corresponding 2-SO2 F dyes.
A further preferred sub-group of compounds of Formula (1) are those of Formula (5); ##STR13## wherein R1 to R4 and R10 to R14 are as herein before defined; and
R15 to R18 each independently is --H, --F, --Cl, --Br, --I, --SO2 F, --NO2, --CN, --NR1 R2, OH or optionally substituted --C1-6 -alkyl or --C1-6 -alkoxy.
The optional substituents for any of the groups represented by R15 to R18 may be selected from any of optional substituents described above for A, D, R1 and R2.
Compositions comprising dispersions of the compounds which are free from water solubilising groups of Formula (1) in which A is an optionally substituted heterocyclic or carbocyclic group; and D is an optionally substituted carbocyclic group; and at least one of A or D carries directly at least one --SO2 F group or carried a substituent to which at least one --SO2 F group is attached in aqueous media are novel and form a further feature of the present invention provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, 4-fluorosulphonylnaphth-1-yl, optionally substituted 1-phenylpyrazol-4-yl-5-one or ##STR14## or that one of A or D does not carry an --NCH2 CH(OH)CH2 Cl, --NCOCH2 Cl or --NCH2 CH2 SO2 F substituent except for
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N-(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-diethylaniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline,
4-(5-fluorosulphonyl-2-chlorophenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(3-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline,
4-(4-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N-ethyl-N-(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-chlorophenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(3-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazonaphth-1-ylamine,
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline,
4-(3-fluorosulphonyl(phenylazo)-3,6-dimethoxyaniline Compositions
comprising dispersions of compounds of Formulae (2), (3), (4), (5) and (7) are also novel. The compositions typically comprise form 1% to 30% of a compound of Formulae (1), (2), (3), (4), (5) or (6) in an aqueous medium. The compositions are preferably buffered at pH 2 to 7 more preferably at pH 4 to 6.
These dispersions may further comprise ingredients conventionally used in dyeing applications such as dispersing agents for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or phenol/cresol/sulphanilic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl ethoxylates which may be sulphonated or phosphated, inorganic salts, de-foamers such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present am from 10% to 200% on the weight of the compound of Formulae (1), (2), (3), (4), (5) or (7). Wetting agents may be used at from 0% to 20% on the weight of the compound (1), (2), (3), (4), (5) or (7). The dispersions may be prepared by bead milling the compound of Formula (1). (2), (3 , (4), (5) or (7) with glass beads or sand in an aqueous medium.
According to a further feature of the present invention there is provided a process for the mass coloration of plastics which comprises incorporating into a plastics material a compound or mixture thereof which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached provided that one of A or D is not 4-fluorosulphonylnaphth-1-yl, except for
4-(2-chloro-4-nitrophenylazo)-2-methyl-4-fluorosulphonylaniline, 4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N-(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-diethylaniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline,
4-(5-fluorosulphonyl-2-chlorophenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(3-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)-3-methylaniline,
4-(4-fluorosulphonylphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N,N-di(2-hydroxyethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazo)-N-ethyl-N-(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-chlorophenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(3-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-methoxyphenylazo)-N-ethyl-N(((2-methoxy)-2-ethoxy)ethyl)aniline,
4-(5-fluorosulphonyl-2-methylphenylazonaphth-1-ylamine,
4-(5-fluorosulphonyl-2-methylphenylazo)-2-ethoxyaniline,
4-(3-fluorosulphonyl(phenylazo)-3,6-dimethoxyaniline,
According to a further feature of the present invention there is provided a process for the mass coloration of plastics which comprises incorporating into a plastics material a compound or mixture thereof which is free from water solubilising groups, of Formula (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly a least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached and at least one of A or D carries directly at least one ester group or carries a substituent to which at least one ester group is attached.
The plastics may be selected from polystyrene, acrylics, styrene/acrylonitrile mixtures, acrylonitrile/butadiene/styrene mixtures, polycarbonate, polyether-sulphone, nylons, rigid PVC (uPVC) and polypropylene.
The compound may be incorporated by blending with granules or powdered plastics material by, for example, dry tumbling or high-speed mixing followed by injection moulding on a screw machine or by conventional compounding/masterbatching techniques. The present dyes generally dissolve or disperse readily in hot plastics melt and provide bright coloration generally with good clarity and good light fastness.
The plastics materials when coloured with the above dyes form a further feature of the present invention.
The compounds of Formula (1) may be obtained by usual methods for the preparation of azo compounds such as by diazotisation of an amine of Formula A--NH2 or A1 --NH2 and coupling onto a component D--X or D1 --X in which A, A1, D and D1 are as hereinbefore defined and X is a group displaceable by a diazotised amine. Typically the amine, A--NH2 or A1 --NH2 may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -10° C. to 10° C. Coupling onto the component D--X or D1 --X may be achieved by adding the diazotised amine to a mixture of D--X or D1 --X in an alkanol such as methanol at a temperature from 0° C. to 10° C. After coupling the compound of Formula (1) may be recovered from the reaction mixture by any convenient means such as by filtration.
Fluorosulphonyl groups may be introduced into the compounds of Formula (1) or Formula (2) or into the A, A1, D and D1 components prior to coupling by methods generally available in the literature. For example reaction of the compound of Formula (1) or Formula (2), A--NH2, A1 --NH2, the NH2 being protected as necessary, D--X or D1 --X, in which A, A1, D and D1 are as hereinbefore defined, with chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 30° C. to 140° C. gives the chlorosulphonyl derivative. The chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative.
Alternatively the compound of Formula (1) or Formula (2), A--NH2, A1 --NH2, D--X or D1 --X may be sulphonated with sulphuric acid or oleum to give the sulphonic acid derivative which may be converted to the chlorosulphonyl derivative by reaction, either of the free acid or an inorganic salt thereof, with thionylchloride optionally in the presence of a chlorophosphorus compound such as phosphorus oxychloride or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 20° C. to 110° C. Similarly a sulphonate ester may be converted to the corresponding chlorosulphonyl derivative. The chlorosulphonyl derivative may then be converted to the fluorosulphonyl derivative as described above.
The compounds of Formulae (1), (2), (3), (4), (5) and (7) are useful for the coloration of synthetic textile materials particularly polyester textile materials and fibre blends thereof to which they impart colours which have excellent wet and light fastness properties.
The compounds of Formula (1), (2), (3), (4), (5) or (7) are also useful for the mass coloration of plastics as described above and impart bright colours generally with good clarity and light fastness.
The invention is further illustrated by the following Examples.
EXAMPLE 1 Preparation of 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-(2-benzoyloxymethyl)aniline
i) Preparation of 2,5-dichloro-4-chlorosulphonylaniline
2,5-Dichloroaniline (32.4 parts) was added portionwise to chlorosulphonic acid (93 parts) at 35° C. The mixture was stirred at 120° C. for 3 hrs and then cooled to 70° C. Dimethyl formamide (1.6 parts) and thionyl chloride (15 parts) were added, maintaining the temperature at 65°-70° C. and the mixture stirred at 70° C. for 24 hours. The reaction mixture was cooled to ambient temperature and poured with caution onto stirred ice (1000 parts) producing a cream precipitate. The product was isolated by filtration, washed acid-free with ice/water and dried under vacuum to yield; 2,5-dichloro-4-chlorosulphonylaniline (44.2 parts).
ii) Preparation of 2,5-dichloro-4-fluorosulphonylaniline
A mixture of 2,5-dichloro-4-chlorosulphonylaniline (44.2 parts), potassium fluoride (38 parts) and water (100 parts) was stirred under reflux for 5 hours. The reaction mixture was cooled to ambient temperature and drowned into water (300 parts). The cream precipitate was isolated by filtration, washed with water and dried under vacuum to yield; 2,5-dichloro-4-fluorosulphonylaniline (37.2 parts).
iii) Preparation of 3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline
Benzoylchloride (3.3 g) was added to a mixture of N-ethyl-N-hydroxyethyl-3-methylaniline (2.1 g) in acetone (25 cm3) and pyridine (1 cm3) and stirred at reflux for 1 hour. The reaction mixture was cooled and used directly in iv) below.
iv) Preparation of 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline
Nitrosyl sulphuric acid (3 cm3 of 40%) was added to a mixture of 2,5-dichloro-4-fluorosulphonylaniline (2 g) in acetic/propionic acid (86:14, 25 cm3) at 0° C. to 5° C. The mixture was stirred at 0° C. to 5° C. for 2 hours before adding the reaction mixture from iii) above in methanol (100 cm3) at 0° C. to 5° C. The precipitated solid was collected by filtration, washed with water, slurried with methanol, collected by filtration and washed with methanol to give 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline (2.1 g) when applied to polyester materials from aqueous dispersion gives bluish-red shades with excellent wet and light fastness properties.
The following examples of dyes of Formula: ##STR15## were prepared by the procedure of Example 1:
__________________________________________________________________________
                                              λmax/                
Ex                                                                        
  R.sup.1   R.sup.2        R.sup.4                                        
                                  R.sup.3                                 
                                       R.sup.6                            
                                              nm                          
__________________________________________________________________________
2 --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OH                                          
                           --NHCOCH.sub.3                                 
                                  --H  --H    522                         
3 --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCOCH.sub.3                                 
                           --NHCOCH.sub.3                                 
                                  --H  --H    518                         
4 --CH.sub.2 CH=CH.sub.2                                                  
            --CH.sub.2 CH=CH.sub.2                                        
                           --NHCOCH.sub.3                                 
                                  --H  --H    520                         
5 --C.sub.4 H.sub.8 OCOCH.sub.3                                           
            --C.sub.4 H.sub.8 OCOCH.sub.3                                 
                           --NHCOCH.sub.3                                 
                                  --H  --H    535                         
6 --C.sub.2 H.sub.4 OCOCH.sub.3                                           
            --C.sub.2 H.sub.4 OCOCH.sub.3                                 
                           --NHCOCH.sub.3                                 
                                  --H  --H    504                         
7 --C.sub.2 H.sub.4 COOCH.sub.3                                           
            --C.sub.2 H.sub.4 COOCH.sub.3                                 
                           --NHCOCH.sub.3                                 
                                  --H  --H    509                         
8 --C.sub.4 H.sub.9                                                       
            --C.sub.2 H.sub.4 COOCH.sub.3                                 
                           --NHCOCH.sub.3                                 
                                  --H  --H    528                         
9 --C.sub.4 H.sub.9                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3                
                           --NHCOCH.sub.3                                 
                                  --H  --H    530                         
10                                                                        
  --C.sub.2 H.sub.4 COOCH.sub.3                                           
            --C.sub.4 H.sub.8 OCOCH.sub.3                                 
                           --NHCOCH.sub.3                                 
                                  --H  --H    526                         
11                                                                        
  --C.sub.2 H.sub.4 OH                                                    
            --C.sub.2 H.sub.4 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    508                         
12                                                                        
  --C.sub.2 H.sub.4 OCOCH.sub.3                                           
            --C.sub.2 H.sub.4 OCOCH.sub.3                                 
                           --H    --OCH.sub.3                             
                                       --H    518                         
13                                                                        
  --C.sub.2 H.sub.4 CN                                                    
            --H            --H    --OCH.sub.3                             
                                       --CH.sub.3                         
                                              504                         
14                                                                        
  --C.sub.2 H.sub.4 CN                                                    
            --H            --CH.sub.3                                     
                                  --H  --H    464                         
15                                                                        
  --C.sub.2 H.sub.4 CN                                                    
            --H            --H    --Cl --H    440                         
16                                                                        
  --C.sub.2 H.sub.4 OCOCH.sub.3                                           
            --C.sub.2 H.sub.4 OCOCH.sub.3                                 
                           --Cl   --H  --H    470                         
17                                                                        
  --C.sub.4 H.sub.8 OCOCH.sub.3                                           
            --C.sub.4 H.sub.8 OCOCH.sub.3                                 
                           --CH.sub.3                                     
                                  --H  --CH.sub.3                         
                                              512                         
18                                                                        
  --C.sub.2 H.sub.4 CN                                                    
            --C.sub.2 H.sub.4 CN                                          
                           --CH.sub.3                                     
                                  --H  --CH.sub.3                         
                                              465                         
19                                                                        
  --C.sub.2 H.sub.4 CN                                                    
            --C.sub.2 H.sub.4 COOCH.sub.3                                 
                           --H    --H  --H    460                         
20                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.4 H.sub.8 OCOCH.sub.3                                 
                           --CH.sub.3                                     
                                  --H  --H    530                         
21                                                                        
  --C.sub.4 H.sub.8 OCOCH.sub.3                                           
            --C.sub.4 H.sub.8 OCOCH.sub.3                                 
                           --CH.sub.3                                     
                                  --H  --H    502                         
22                                                                        
  --C.sub.2 H.sub.4 OCOCH.sub.3                                           
            --C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                          
                           --H    --OCH.sub.3                             
                                       --NHCOCH.sub.3                     
                                              548                         
23                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    520                         
24                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.4 H.sub.8 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    530                         
25                                                                        
  --C.sub.2 H.sub.5                                                       
            --CH.sub.2 CH(CH)C.sub.2 H.sub.5                              
                           --CH.sub.3                                     
                                  --H  --H    532                         
26                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.5                                             
                           --H    --OCH.sub.3                             
                                       --CH.sub.3                         
                                              548                         
27                                                                        
  --C.sub.2 H.sub.5                                                       
            --CH.sub.2 C(OH) (OC.sub.2 H.sub.5)                           
                           --CH.sub.3                                     
                                  --H  --H    525                         
28                                                                        
  --C.sub.2 H.sub.5                                                       
            --CH.sub.8 C(OH) (CN)                                         
                           --CH.sub.3                                     
                                  --H  --H    523                         
29                                                                        
  --C.sub.5 H.sub.11                                                      
            --C.sub.2 H.sub.4 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    529                         
30                                                                        
  --C.sub.2 H.sub.4 OCH.sub.3                                             
            --C.sub.2 H.sub.4 OCH.sub.3                                   
                           --CH.sub.3                                     
                                  --H  --H    520                         
31                                                                        
  --C.sub.4 H.sub.9                                                       
            --C.sub.2 H.sub.4 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    528                         
32                                                                        
  --C.sub.6 H.sub.13                                                      
            --C.sub.2 H.sub.4 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    531                         
33                                                                        
  --C.sub.2 H.sub.4 Ophenyl                                               
            --C.sub.2 H.sub.4 OH                                          
                           --CH.sub.3                                     
                                  --H  --H    520                         
34                                                                        
  --CH.sub.2 C(CN) (OC.sub.2 H.sub.5)                                     
            --CH.sub.2 C(CN) (OC.sub.2 H.sub.5)                           
                           --CH.sub.3                                     
                                  --H  --H    517                         
35                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COOC.sub.2 H.sub.4         
            OCH.sub.3      --CH.sub.3                                     
                                  --H  --H    525                         
36                                                                        
  --CH.sub.3                                                              
            --CH.sub.3     --H    --H  --H    515                         
37                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.5                                             
                           --H    --H  --H    520                         
38                                                                        
  --C.sub.3 H.sub.7                                                       
            --C.sub.3 H.sub.7                                             
                           --H    --H  --H    522                         
39                                                                        
  --C.sub.4 H.sub.9                                                       
            --C.sub.4 H.sub.9                                             
                           --H    --H  --H    527                         
40                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.5                                             
                           --NHCOCH.sub.3                                 
                                  --H  --H    536                         
41                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCOphenyl                                   
                           --CH.sub.3                                     
                                  --H  --H    514                         
42                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                          
                           --CH.sub.3                                     
                                  --H  --H    514                         
43                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3                
                           --CH.sub.3                                     
                                  --H  --H    513                         
44                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OC.sub.4 H.sub.9         
                           --CH.sub.3                                     
                                  --H  --H    513                         
45                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.2 tetra                           
                           --CH.sub.3                                     
                                  --H  --H    512                         
            hydrofuran-2-yl                                               
46                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 Ophenyl                  
                           --CH.sub.3                                     
                                  --H  --H    512                         
47                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.2 COOC.sub.2 H.sub.5              
                           --CH.sub.3                                     
                                  --H  --H    511                         
48                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4         
            OCH.sub.3      --CH.sub.3                                     
                                  --H  --H    513                         
49                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4         
            OC.sub.2 H.sub.5                                              
                           --CH.sub.3                                     
                                  --H  --H    513                         
50                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OC.sub.2 H.sub.5         
                           --CH.sub.3                                     
                                  --H  --H    512                         
51                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH(CH.sub.3).sub.2                       
                           --CH.sub.3                                     
                                  --H  --H    513                         
52                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OH                       
                           --CH.sub.3                                     
                                  --H  --H    514                         
53                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.2 tetra                           
                           --CH.sub.3                                     
                                  --H  --H    512                         
            hydropyran-2-yl                                               
54                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.3 phenyl                          
                           --CH.sub.3                                     
                                  --H  --H    513                         
55                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.3 H.sub.6 COOC.sub.2 H.sub.5       
                           --CH.sub.3                                     
                                  --H  --H    514                         
56                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5    
                           --CH.sub.3                                     
                                  --H  --H    514                         
57                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.4 H.sub.8 OH                       
                           --CH.sub.3                                     
                                  --H  --H    514                         
58                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.4 H.sub.8 OCOCH.sub.3              
                           --CH.sub.3                                     
                                  --H  --H    513                         
59                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.2 COOCH.sub.3                     
                           --CH.sub.3                                     
                                  --H  --H    511                         
60                                                                        
  --C.sub.2 H.sub.4 OH                                                    
            --C.sub.2 H.sub.4 COOCH.sub.2 tetra                           
                           --CH.sub.3                                     
                                  --H  --H    511                         
            hydrofuran-2-yl                                               
61                                                                        
  --C.sub.2 H.sub.4 OH                                                    
            --C.sub.2 H.sub.4 COOCH.sub.2 COOC.sub.2 H.sub.5              
                           --CH.sub.3                                     
                                  --H  --H    510                         
62                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.2 CN                              
                           --CH.sub.3                                     
                                  --H  --H    512                         
63                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 CN                       
                           --CH.sub.3                                     
                                  --H  --H    514                         
64                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 COOCH.sub.2 COCH.sub.3                      
                           --CH.sub.3                                     
                                  --H  --H    513                         
65                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCOC(CH.sub.3).sub.3                        
                           --CH.sub.3                                     
                                  --H  --H    511                         
66                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCO(CH.sub.2).sub.3 CH.sub.3                
                           --CH.sub.3                                     
                                  --H  --H    510                         
67                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC0CH(CH.sub.3).sub.2                       
                           --CH.sub.3                                     
                                  --H  --H    510                         
68                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCO(CH.sub.2).sub.3 Cl                      
                           --CH.sub.3                                     
                                  --H  --H    507                         
69                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC0(4-NO.sub.2 phenyl)                      
                           --CH.sub.3                                     
                                  --H  --H    503                         
70                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCO(4-CH.sub.3 phenyl)                      
                           --CH.sub.3                                     
                                  --H  --H    511                         
71                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCO(3-CH.sub.3 phenyl)                      
                           --CH.sub.3                                     
                                  --H  --H    511                         
72                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 O(4-OCH.sub.3 phenyl)                       
                           --CH.sub.3                                     
                                  --H  --H    512                         
73                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 O(2-OCH.sub.3 phenyl)                       
                           --CH.sub.3                                     
                                  --H  --H    509                         
74                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COOC.sub.2 H.sub.5         
                           --CH.sub.3                                     
                                  --H  --H    521                         
75                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COOCH.sub.3                
                           --CH.sub.3                                     
                                  --H  --H    521                         
76                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COOCH.sub.2 COOC.sub.2     
            H.sub.5        --CH.sub.3                                     
                                  --H  --H    521                         
77                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCOC.sub.2 H.sub.4 COOC.sub.2 H.sub.5       
                           --CH.sub.3                                     
                                  --H  --H    511                         
78                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OCOCH.sub.2 Ophenyl                         
                           --CH.sub.3                                     
                                  --H  --H    515                         
79                                                                        
  --C.sub.2 H.sub.4 OH                                                    
            --C.sub.2 H.sub.4 OCOphenyl                                   
                           --CH.sub.3                                     
                                  --H  --H    517                         
80                                                                        
  --C.sub.2 H.sub.4 COOC.sub.3 H.sub.7                                    
            --C.sub.2 H.sub.4 COOC.sub.3 H.sub.7                          
                           --NHCOCH.sub.3                                 
                                  --H  --H    498                         
81                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.3 H.sub.6 COOC.sub.2 H.sub.5                          
                           --CH.sub.3                                     
                                  --H  --H    523                         
82                                                                        
cyclohexyl                                                                
  --CH.sub.2 phenyl                                                       
            --H            --H    --H  509                                
83                                                                        
  --C.sub.4 H.sub.9                                                       
            --CH(CH.sub.3).sub.2                                          
                           --NHCOCH.sub.3                                 
                                  --H  --H    539                         
84                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.4 H.sub.9                                             
                           --NHCOCH.sub.3                                 
                                  --H  --H    539                         
85                                                                        
  --C.sub.2 H.sub.5                                                       
            --C.sub.2 H.sub.4 OC.sub.2 H.sub.4 COOC.sub.2 H.sub.4         
            OCH.sub.3      --CH.sub.3                                     
                                  --H  --H    525                         
86                                                                        
  --C.sub.2 H.sub.4 OH                                                    
            --C.sub.2 H.sub.4 Ophenyl                                     
                           --CH.sub.3                                     
                                  --H  --H    520                         
__________________________________________________________________________
EXAMPLE 87 Preparation of 4-(2,6-dibromo-4-fluorosulphonylphenylazo)-3-acetamido-N-N-diethylaniline
i) Preparation of 2,6-dibromo-4-fluorosulphonylaniline
To a solution of 4-aminobenzenesulphonyl fluoride (10 parts) in acetic acid (100 parts), stirring at 0°-5° C., was added gradually a solution of bromine (18 parts) in acetic acid (50 parts); keeping the temperature below 5° C. The temperature was allowed to warm to ambient and the mixture was stirred at this temperature for a further 1 hr. The reaction mass was drowned into water (500 parts), the product was isolated by filtration, washed with cold water and dried at 50° C. to yield; 2,6-dibromo-4-fluorosulphonylaniline (17.5 parts).
ii) Preparation of 4-(2,6-dibromo-4-fluorosulphonylphenylazo)-3-acetamido-N-N-diethylaniline
A mixture of 2,6-dibromo-4-fluorosulphonylaniline (2.7 parts) and acetic/propionic acid mixture (15 parts, 86/14 vol/vol) was stirred and heated until a complete solution was formed. The solution was set stirring at 0°-5° C., and nitrosyl sulphuric acid soln (5 parts) was added dropwise. The mixture was stirred at this temperature for a further 30 min.
The diazo solution was added slowly to a mixture of 3-N,N-diethylaminoacetanilide (1.7 parts), methanol (50 parts) and sulphamic acid (0.5 parts); stirring at 0°-5° C. After stirring for 1 hr at this temperature, water (50 parts) was added and the mixture was stirred a further 30 min at ambient temperature. The product was isolated by filtration, washed with water and methanol and then dried at 50° C. to yield; 4-(2,6-dibromo-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (1.8 parts) λmax=480 nm.
When applied to polyester materials from an aqueous dispersion, the dye gives dull orange shades with excellent light fastness and excellent fastness to wet treatments. The following examples of dyes of Formula: ##STR16## were prepared by the procedure of Example 87
__________________________________________________________________________
                                   λmax/                           
Ex. R.sup.1 R.sup.2  R.sup.4                                              
                            R.sup.3                                       
                                R.sup.6                                   
                                   nm                                     
__________________________________________________________________________
88  --C.sub.2 H.sub.4 OH                                                  
            --C.sub.2 H.sub.4 OC.sub.2 H.sub.5                            
                     --H    --H --H                                       
                                   434                                    
89  --C.sub.2 H.sub.4 OCH.sub.3                                           
            --C.sub.2 H.sub.4 OCH.sub.3                                   
                     --CH.sub.3                                           
                            --H --H                                       
                                   447                                    
90  --C.sub.2 H.sub.4 CN                                                  
            --C.sub.2 H.sub.4 CN                                          
                     --CH.sub.3                                           
                            --H --H                                       
                                   418                                    
91  --C.sub.2 H.sub.5                                                     
            --C.sub.2 H.sub.4 CN                                          
                     --CH.sub.3                                           
                            --H --H                                       
                                   435                                    
92  --H     --C.sub.2 H.sub.4 CN                                          
                     --H    --H --H                                       
                                   399                                    
93  --C.sub.2 H.sub.5                                                     
            --C.sub.2 H.sub.4 CN                                          
                     --H    --H --H                                       
                                   421                                    
94  --C.sub.2 H.sub.4 OH                                                  
            --C.sub.2 H.sub.4 CN                                          
                     --H    --H --H                                       
                                   420                                    
95  --C.sub.2 H.sub.4 CN                                                  
            --C.sub.2 H.sub.4 CN                                          
                     --H    --H --H                                       
                                   406                                    
96  --C.sub.2 H.sub.5                                                     
            --C.sub.2 H.sub.5                                             
                     --H    --H --H                                       
                                   438                                    
97  --C.sub.2 H.sub.5                                                     
            --C.sub.2 H.sub.5                                             
                     --CH.sub.3                                           
                            --H --H                                       
                                   453                                    
98  --C.sub.2 H.sub.4 OH                                                  
            --C.sub.2 H.sub.4 OH                                          
                     --CH.sub.3                                           
                            --H --H                                       
                                   454                                    
99  --C.sub.4 H.sub.9                                                     
            --C.sub.4 H.sub.9                                             
                     --H    --H --H                                       
                                   442                                    
100 --C.sub.2 H.sub.5                                                     
            --CH.sub.2 phenyl                                             
                     --H    --H --H                                       
                                   431                                    
101 --C.sub.2 H.sub.5                                                     
            --C.sub.2 H.sub.5                                             
                     --NHCOCH.sub.3                                       
                            --H --H                                       
                                   486                                    
102 --C.sub.4 H.sub.9                                                     
            --C.sub.4 H.sub.9                                             
                     --NHCOCH.sub.3                                       
                            --H --H                                       
                                   486                                    
103 --C.sub.4 H.sub.8 OCOCH.sub.3                                         
            --C.sub.4 H.sub.9 OCOCH.sub.3                                 
                     --NHCOCH.sub.3                                       
                            --H --H                                       
                                   479                                    
__________________________________________________________________________
EXAMPLE 104 Preparation of 4-(2,6-dicyano-4-fluorosulphonyphenylazo)-3-acetamido-N-N-diethylaniline
A mixture of 4-(2,6-dibromo-4-fluorosulphonylphenyllazo-3-acetamido-N,N-diethylaniline (Example 101) (1.5 parts), cuprous cyanide (0.54 parts) and dimethylformamide (20 parts) was stirred at ambient temperature for 3 hr. The reaction mixture was diluted with water (40 parts), stirred for 30 min and the product was isolated by filtration to yield; 4-(2,6-dicyano-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (0.8 parts) λmax=611 nm.
When applied to polyester materials from an aqueous dispersion, the dye gives bright blue shades with excellent light fastness and excellent fastness to wet treatments.
EXAMPLE 105 Preparation of 4-(2,6-dicyano-4-fluorosulphonylphenylazo)-3-acetamido-N-N-di-n-butyl aniline
The dye in Example 102 (3.09 g) was stirred in DMF (30 cm3) and CuCN (1.0 g) at 90° C. for 2 hours. The reaction mix was drowned onto ice and the precipitate collected, washed with water and dried under suction. The filter cake was dissolved in dichloromethane, filtered and the filtrate evaporated to give a blue dye (λmax 611 nm).
EXAMPLE 106 Preparation of 4-(2,6-dicyano-4-fluorosulphonylphenylazo)-3-acetamido-N-N-diacetoxybutylamino aniline
The dye in Example 103 (3.09 g) was stirred in DMF (30 cm3) and CuCN (1.0 g) at 90° C. for 2 hours. The reaction mix was drowned onto ice and the precipitate collected, washed with water and dried under suction. The filter cake was dissolved in dichloromethane, filtered and the filtrate evaporated to give a blue dye (λmax 608 nm).
EXAMPLE 107 Preparation of 4-(2,6-dichloro-4-fluorosulphonylphenylazo)-N-N-di-n-butylaniline
i) Preparation of 2,6-dichloro-4-chlorosulphonylaniline
The procedure of Example 1 ii) was repeated except that in place of the 32.4 parts of 2,5-dichloraniline, 32.4 parts of 2,6-dichloroaniline were used, to yield 2,6-dichloro-4-chlorosulphonylaniline (42.6 parts).
ii) Preparation of 2,6-dichloro-4-fluorosulphonylaniline
The procedure of Example iii) was repeated except that in place of the 44.2 parts of 2,5-dichloro-4-chlorosulphonylaniline, 42.6 parts of 2,6-dichloro-4-chlorosulphonylaniline were used, to yield 2,6-dichloro-4-fluorosulphonylaniline (36.0 parts).
iii) Preparation of 4-(2,6-dichloro-4-fluorosulphonylphenylazo)-N-N-di-n-butylaniline
A mixture of 2,6-dichloro-4-fluorosulphonylaniline (2.0 parts) and acetic/propionic acid mixture (15 parts, 86/14 vol/vol) was stirred and heated until a complete solution was formed. The solution was set stirring at 0°-5° C. and nitrosyl sulphuric acid solution (5 parts) was added slowly. The mixture was stirred at this temperature for a further 30 min. The cooled diazo solution was added slowly to a mixture of N,N-di-n-butylaniline (1.7 parts), methanol (40 parts) and sulphamic acid (0.5 parts); stirring at 0°-5° C. After stirring for 3 hr at this temperature, water (50 parts) was added and the mixture stirred for a further 2 hr at ambient. The product was isolated by filtration, washed with water and methanol and dried to yield; 4-(2,6-dichloro-4-fluorosulphonylphenylazo)-N,N-di-n-butylaniline (3.0 parts) λmax=443 nm. When applied to polyester materials from an aqueous dispersion, the dye gives dull yellow brown shades with excellent fastness to light and wet treatments.
The following examples of dyes of Formula: ##STR17## were prepared by the procedure of Example 107
______________________________________                                    
Example                                                                   
       R.sup.1 R.sup.2    R.sup.4                                         
                                R.sup.3                                   
                                     R.sup.6                              
                                          λmax/nm                  
______________________________________                                    
108    --C.sub.2 H.sub.5                                                  
               --C.sub.2 H.sub.5                                          
                          --H   --H  --H  439                             
109    --C.sub.2 H.sub.5                                                  
               --C.sub.2 H.sub.5                                          
                          --CH.sub.3                                      
                                --H  --H  455                             
110    --C.sub.2 H.sub.5                                                  
               --CH.sub.2 phenyl                                          
                          --H   --H  --H  431                             
______________________________________
EXAMPLE 111 Preparation of 4-(2-bromo-4-fluorosulphonylphenylazo)-3-acetamido-N-N-diethylaniline
The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6-dibromo-4-fluorosulphonylaniline; 2.0 parts of 2-bromo-4-fluorosulphonylaniline were used. The product, 4-(2-bromo-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (1.6 parts) λmax=524 nm, when applied to polyester materials from an aqueous dispersion gives bright mid red shades with excellent fastness to light and wet treatments.
EXAMPLE 112 Preparation of 4-(2,5-dimethoxy-4-fluorosulphonylphenylazo)-3-acetamido-N-N-diethylanilin
The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6-dibromo-4-fluorosulphonylaniline; 1.9 parts of 2,5-dimethoxy-4-fluorosulphonylaniline were used. The product, 4-(2,5-dimethoxy-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (1.4 parts) λmax=545 nm, when applied to polyester materials from an aqueous dispersion gives bluish red shades with excellent fastness to light and wet treatments.
EXAMPLE 113 Preparation of 4-(2-nitro-5-chloro-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline
The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6-dibromo-4-fluorosulphonylaniline; 2.0 parts of 2-nitro-5-chloro-4-fluorosulphonylaniline were used. The product, 4-(2-nitro-5-chloro-4-fluorosulphonylphenylazo)-3-acetamido-N,N-diethylaniline (2.6 parts) λmax=550 nm, when applied to polyester materials from an aqueous dispersion gives bluish red shades with excellent fastness to light and wet treatments.
EXAMPLE 114
i) Preparation of 2-nitro-4-fluorosulphonylaniline
N-acetyl sulphanilyl chloride (100 g) was dissolved in concentrated sulphuric acid (515 cm3), cooled to 4° C. and a mixture of concentrated nitric acid (38.6 cm3) and concentrated sulphuric acid (42.9 cm3) added dropwise maintaining the temperature at 4°-6° C. After 1 hour the reaction mix was drowned onto ice and the precipitate collected, extracted into dichloromethane and evaporated to a yellow solid (92 g). 31 g of this yellow solid was refluxed for 3 hours in water (20 cm3), p-dioxane (20 cm3) and KF (19.4 g) then drowned onto ice and the precipitate collected. This precipitate was refluxed in absolute ethanol (35 cm3) and concentrated hydrochloric acid (35 cm3) for 1 hour then drowned onto ice, filtered and suction dried. Recrystallisation from ethanol yielded 8.7 g of the required compound.
ii) 2-Nitro-4-fluorosulphonyl aniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N,N-diethylamino)acetanilide (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered, washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 541 nm and gives good fastness to washing, light and heat. The following examples of dyes of Formula: ##STR18## were prepared by the procedure of Example 114
__________________________________________________________________________
Example                                                                   
     R.sup.4  R.sup.1  R.sup.2   R.sup.5                                  
                                      λmax/nm                      
__________________________________________________________________________
115  --NHCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --H  541                                 
116  --NHCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --OCH.sub.3                              
                                      590                                 
117  --NHCOCH.sub.3                                                       
              --C.sub.2 H.sub.4 OCOCH.sub.3                               
                       --C.sub.2 H.sub.4 OCOCH.sub.3                      
                                 --OCH.sub.3                              
                                      564                                 
118  --CH.sub.3                                                           
              --C.sub.4 H.sub.8 OCOCH.sub.3                               
                       --C.sub.4 H.sub.5 OCOCH.sub.3                      
                                 --H  530                                 
119  --NHCOCH.sub.3                                                       
              --C.sub.4 H.sub.9                                           
                       --CH(CH.sub.3)C.sub.2 H.sub.5                      
                                 --H  546                                 
120  --NHCOCH.sub.3                                                       
              --C.sub.4 H.sub.9                                           
                       --C.sub.4 H.sub.9                                  
                                 --OCH.sub.3                              
                                      591                                 
121  --NHCOCH.sub.3                                                       
              --C.sub.5 H.sub.11                                          
                       --C.sub.5 H.sub.11                                 
                                 --OCH.sub.3                              
                                      593                                 
122  --NHCOC.sub.2 H.sub.5                                                
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --OCH.sub.2                              
                                      592                                 
123  --NHCOC.sub.3 H.sub.7                                                
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --OCH.sub.3                              
                                      592                                 
124  --NHCOCH(CH.sub.3).sub.2                                             
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --OCH.sub.3                              
                                      591                                 
125  --NHCOC.sub.4 H.sub.9                                                
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --OCH.sub.3                              
                                      593                                 
126  --OC.sub.4 H.sub.9                                                   
              --C.sub.4 H.sub.9                                           
                       --C.sub.4 H.sub.9                                  
                                 --OCH.sub.3                              
                                      575                                 
127  --HNCOCH.sub.3                                                       
              --C.sub.3 H.sub.7                                           
                       --C.sub.3 H.sub.7                                  
                                 --OCH.sub.3                              
                                      594                                 
128  --HNSO.sub.2 CH.sub.3                                                
              --C.sub.3 H.sub.7                                           
                       --C.sub.3 H.sub.7                                  
                                 --OCH.sub.3                              
                                      562                                 
129  --HNCOCH(CH.sub.3).sub.2                                             
              --C.sub.3 H.sub.7                                           
                       --C.sub.3 H.sub.7                                  
                                 --OCH.sub.3                              
                                      591                                 
130  --HNCOCH.sub.3                                                       
              --C.sub.3 H.sub.7                                           
                       --CH(CH.sub.3).sub.2                               
                                 --OCH.sub.3                              
                                      590                                 
131  --HNCOCH.sub.3                                                       
              --CH(CH.sub.3)CH.sub.2 CH.sub.3                             
                       --H       --OCH.sub.3                              
                                      565                                 
132  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.3 H.sub.7 (4-SO.sub.2 F                    
                                 --OCH.sub.3                              
                                      585                                 
                       phenyl)                                            
133  --HNCOCH.sub.3                                                       
              --C.sub.3 H.sub.7 (4-SO.sub.2 F                             
                       --C.sub.3 H.sub.7 (4-SO.sub.2 F                    
                                 --OCH.sub.3                              
                                      580                                 
              phenyl)  phenyl)                                            
134  --HNCOC(CH.sub.3).sub.3                                              
              --C.sub.2 H.sub.5                                           
                       --H       --OCH.sub.3                              
                                      566                                 
135  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.4 COOC.sub.3 H.sub.7                        
                       --C.sub.2 H.sub.4 COOC.sub.3 H.sub.7               
                                 --H  524                                 
136  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.4 H.sub.8 COOC(CH.sub.3).sub.3             
                                 --OCH.sub.3                              
                                      591                                 
137  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.4 (phenyl)                         
                                 --OCH.sub.3                              
                                      588                                 
138  --HNSO.sub.2 phenyl                                                  
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                 --OCH.sub.3                              
                                      573                                 
__________________________________________________________________________
EXAMPLE 139
i) Preparation of 2-nitro-4-fluorosulphonyl-6-chloroaniline
2-Nitro-4-fluorosulphonylaniline (10 g) was dispersed in 30% HCl (63.6 g), cooled to 0°-5° C. and sodium chlorate (2 g) dissolved in water (3.6 g) added dropwise ensuring maintaining the temperature at 0°-5° C. After 30 minutes reaction mixture drowned onto ice and precipitate collected, washed with water and suction dried to yield 8.5 g of 2-Nitro-4-fluorosulphonyl-6-chloroaniline.
ii) 2-Nitro-4-fluorosulphonyl-6-chloroaniline (7.86 mmol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (7.86 mmol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N,N-diethylamino)acetanilide (7.86 mmol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 550 nm and gives good fastness to washing, light and heat.
The following examples of dyes of Formula: ##STR19## were prepared by the procedure of Example 139
__________________________________________________________________________
                                       λmax                        
Example                                                                   
     R.sup.4  R.sup.1  R.sup.2    R.sup.5                                 
                                       (nm)                               
__________________________________________________________________________
140  --NHCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                  --H  550                                
141  --NHCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.5                                  
                                  --OCH.sub.3                             
                                       606                                
142  --CH.sub.3                                                           
              --C.sub.4 H.sub.8 OCOCH.sub.3                               
                       --C.sub.4 H.sub.8 OCOCH.sub.3                      
                                  --H  545                                
143  --CH.sub.3                                                           
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.4 OCOCH.sub.3                      
                                  --H  535                                
144  --NHCOCH.sub.3                                                       
              --C.sub.4 H.sub.9                                           
                       --C.sub.4 H.sub.9                                  
                                  --OCH.sub.3                             
                                       604                                
145  --HNCOCH.sub.3                                                       
              --C.sub.3 H.sub.7                                           
                       --C.sub.3 H.sub.7                                  
                                  --OCH.sub.3                             
                                       610                                
146  --HNCOC(CH.sub.3).sub.3                                              
              --C.sub.2 H.sub.5 COOCH.sub.3                               
                       --C.sub.2 H.sub.5 COOCH.sub.3                      
                                  --OCH.sub.3                             
                                       545                                
147  --HNSO.sub.2 CH.sub.3                                                
              --C.sub.3 H.sub.7                                           
                       --C.sub.3 H.sub.7                                  
                                  --OCH.sub.3                             
                                       588                                
148  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.3 H.sub.7                                  
                                  --CH.sub.3                              
                                       565                                
149  --HNCOCH.sub.3                                                       
              --CH(CH.sub.3).sub.2                                        
                       --C.sub.3 H.sub.7                                  
                                  --OCH.sub.3                             
                                       602                                
150  --HNCOCH(CH.sub.3).sub.2                                             
              --C.sub.3 H.sub.7                                           
                       --C.sub.3 H.sub.7                                  
                                  --OCH.sub.3                             
                                       608                                
151  --HNCOCH.sub.3                                                       
              --C.sub.4 H.sub.9                                           
                       --C.sub.2 H.sub.5 COOC.sub.2 H.sub.4 OCH.sub.3     
                                  --OCH.sub.3                             
                                       603                                
152  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --CH.sub.3 --OCH.sub.3                             
                                       601.5                              
153  --HNCOC(CH.sub.3).sub.3                                              
              --H      --C.sub.2 H.sub.5 COOC.sub.3 H.sub.7               
                                  --OCH.sub.3                             
                                       565                                
154  --HNCOC(CH.sub.3).sub.3                                              
              --C.sub.2 H.sub.4 COOC.sub.3 H.sub.7                        
                       --C.sub.2 H.sub.4 COOC.sub.3 H.sub.7               
                                  --OCH.sub.3                             
                                       574                                
155  --HNCOCH.sub.3                                                       
              --C.sub.2 H.sub.5                                           
                       --C.sub.2 H.sub.4 (phenyl)                         
                                  --OCH.sub.3                             
                                       607                                
__________________________________________________________________________
EXAMPLE 156 Preparation of 4-(5-chloro-4-fluorosulphonyl-2-nitrophenylazo)-3-acetamido-6-methoxy-N-N-dibutylaniline
i) 2-Nitro-5-chloroacetanilide (10 g) was added cautiously to chlorosulphonic acid (40 cm3) then heated at 120° C. for 2 hours. The reaction mix was cooled to 50° C. and drowned onto ice. The precipitate was filtered, washed with a little water and suction dried. This solid was dispersed in water (20 cm3), p-dioxane (20 cm3) and KF (10 g). After refluxing for 2 hours the reaction mix was drowned into water, the precipitate filtered and suction dried. This solid was refluxed in water (50 cm3) and 36% HCl (50 cm3) for 1 hour, drowned onto ice and the precipitate collected. Yield 3.5 g.
ii) 2-Nitro-4-fluorosulphonyl-5-chloroaniline (7.86 mmol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (7.86 mmol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N,N-dibutylamino)-4-methoxyacetanilide (7.86 mmol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 604 nm and gives good fastness to washing, light and heat.
EXAMPLE 157 Preparation of 4-(2-nitro-4-fluorosulphonyl-6-bromophenylazo)-3-acetamido-N-N-diethylaniline
i) 2-Nitro-4-fluorosulphonylaniline (5 g) was dissolved in glacial acetic acid (50 cm3) and bromine (4.4 g) added. Reaction mix warmed to 75° C. for 2 hours then drowned onto ice, filtered, washed with water and suction dried. Yield 6.5 g of yellow solid.
ii) 2-Nitro-4-fluorosulphonyl-6-bromoaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N,N-diethylamino)acetanilide (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 550 nm and gives good fastness to washing, light and heat.
The following dyes of Formula ##STR20## were prepared by the procedure of Example 157
__________________________________________________________________________
Example                                                                   
      R.sup.4 R.sup.1 R.sup.2  R.sup.5                                    
                                   λmax                            
__________________________________________________________________________
158   --NHCOCH.sub.3                                                      
              --C.sub.2 H.sub.4 OCOCH.sub.3                               
                      --C.sub.2 H.sub.4 OCOCH.sub.3                       
                               --H 530                                    
159   --NHCOCH.sub.3                                                      
              --C.sub.4 H.sub.9                                           
                      --CH(CH.sub.3)C.sub.2 H.sub.5                       
                               --H 556                                    
160   --NHCOCH.sub.3                                                      
              --C.sub.4 H.sub.9                                           
                      --C.sub.4 H.sub.9                                   
                               --H 555                                    
__________________________________________________________________________
EXAMPLE 162 Preparation of 4-(2-nitro-4-fluorosulphonyl-6-cyanophenylazo)-3-acetamido-N-N-diethylaniline
Dye Example 157 (2.0 g) was stirred at 90° C. with CuCN (0.42 g) and DMF (20 cm3) for 3 hours. The reaction mix was drowned onto ice (50 g) and the precipitate collected, washed with water and suction dried. The filter cake was slurried in dichloromethane, filtered and the filtrate evaporated to give a solid dye (λmax 603 nm) which gives good fastness to heat, washing and light.
The following dyes of Formula ##STR21## were prepared by the procedure of Example 162
__________________________________________________________________________
Example                                                                   
      R.sup.4 R.sup.1 R.sup.2  R.sup.5                                    
                                   λmax                            
__________________________________________________________________________
163   --NHCOCH.sub.3                                                      
              --C.sub.2 H.sub.4 OCOCH.sub.3                               
                      --C.sub.2 H.sub.4 OCOCH.sub.3                       
                               --H 585                                    
164   --NHCOCH.sub.3                                                      
              --C.sub.4 H.sub.9                                           
                      --CH(CH.sub.3)C.sub.2 H.sub.5                       
                               --H 607                                    
165   --NHCOCH.sub.3                                                      
              --C.sub.4 H.sub.9                                           
                      --C.sub.4 H.sub.9                                   
                               --H 606                                    
__________________________________________________________________________
EXAMPLE 166 Preparation of 4-(3-carboethoxy-5-nitrothien-2-ylazo)-3-methyl-N-ethyl-N-(3-fluorosulphonylbenzoyloxyethylaniline
4-(3-carboethoxy-5-nitrothienyl-2-ylazo)-3-methyl-N-ethyl-N-hydroxyethyl aniline (5 mmol) was disolved in chloroform (20 cm3), potassium carbonate (0.7 g) and 3-fluorosulphonylbenzoylchloride (12 g) were added and the mixture refluxed for 2 hours. The reaction mixture was filtered and the filtrate evaporated to leave the solid dye, λmax=588 nm.
The following examples of dyes of Formula ##STR22## were prepared by the procedure of Example 166
__________________________________________________________________________
Example                                                                   
     R.sup.1                                                              
           R.sup.2      R.sup.6                                           
                            R.sup.7                                       
                                  λmax/nm                          
__________________________________________________________________________
167  --C.sub.2 H.sub.5                                                    
           --C.sub.4 H.sub.8 OCO(3-SO.sub.2 Fphenyl)                      
                        --CH.sub.3                                        
                            --COOC.sub.2 H.sub.5                          
                                  616                                     
168  --C.sub.2 H.sub.4 CN                                                 
           --C.sub.2 H.sub.4 OCO(3-SO.sub.2 Fphenyl)                      
                        --H --NO.sub.2                                    
                                  575                                     
169  --C.sub.2 H.sub.4 CN                                                 
           --C.sub.2 H.sub.4 OCO(3-SO.sub.2 Fphenyl)                      
                        --CH.sub.3                                        
                            --NO.sub.2                                    
                                  594                                     
170  --C.sub.2 H.sub.4 CN                                                 
           --C.sub.2 H.sub.4 OCO(3-SO.sub.2 Fphenyl)                      
                        --H --COOC.sub.2 H.sub.5                          
                                  575                                     
171  --C.sub.2 H.sub.4 CN                                                 
           --C.sub.2 H.sub.4 OCO(3-SO.sub.2 Fphenyl)                      
                        --H --COCH.sub.3                                  
                                  563                                     
__________________________________________________________________________
EXAMPLE 172 Preparation of 4-(3-carboethoxy-5-nitrothien-2-ylazo)-3-methyl-N-ethyl-N-(4-fluorosulphonylphenyl)methyl aniline
2-Amino-3-carboethoxy-5-nitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14, 25 cm3), cooled to 0°-5° C. and nitrosylsulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-ethyl-N-(4-fluorosulphonylbenzyl)-3-toluidine (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 580 nm and gives good fastness to washing, light and heat.
The N-ethyl-N-(4-fluorosulphonylbenzyl)-3-toluidine was prepared as follows: N-Ethyl-3-toluidine (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm3) and 4-fluorosulphonylbenzyl bromide (0.2 mol) were stirred at 100° C. for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (22 g). No further purification was required.
The 4-fluorosulphonylbenzylbromide was prepared as follows: Tosyl chloride (50 g), bromine (43 g) and carbon tetrachloride (500 mls) were stirred at reflux while shining a UV lamp (365 nm) onto the reaction. Once the solution became colourless the reaction was stopped and the solvent removed by evaporation. The resultant oil was refluxed in water (200 mls) and potassium fluoride (47 g) for three hours. After three hours the reaction mix was drowned onto ice (500 g) and the precipitate collected, washed with water and dried in vacuo. Yield 34 g of pale yellow crystals which by GLC is 54% required material, 17% starting material and 12% dibrominated species.
EXAMPLE 173 Preparation of 4-(3-carboethoxy-5-nitrothien-2-ylazo)-N-ethyl-N-(4-fluorosulphonylphenyl)methylaniline
2-Amino-3-carboethoxy-5-nitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-(4-fluorosulphonylbenzyl)-N-ethylaniline (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 560 nm and gives good fastness to washing, light and heat.
The N-ethyl-N-(4-fluorosulphonylbenzyl)aniline was prepared as follows:
N-Ethylaniline (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm3) and 4-fluorosulphonylbenzyl bromide (0.2 mol) were stirred at 100° C. for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (20 g). No further purification was required.
EXAMPLE 174 Preparation of 4-(3-carboethoxy-5-nitrothien-2-ylazo)-N-ethyl-N(4-fluorosulphonylphenyl)propylaniline
2-Amino-3-carboethoxy-5-nitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-(4-fluorosulphonylphenylpropyl)-N-ethylaniline (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 593 nm and gives good fastness to washing, light and heat.
The N-ethyl-N-(4-fluorosulphonylphenylpropyl)aniline was prepared as follows:
N-Ethylaniline (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm3) and 4-fluorosulphonylphenylpropyl bromide (0.2 mol) were stirred at 100° C. for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (25 g). No further purification was required.
The 4-fluorosulphonylphenylpropylbromide was prepared as follows:
Phenylpropyl bromide (19.9 g) was dissolved in chloroform (500 mls) and chlorosulphonic acid (116 g) added dropwise. Stirred for 12 hours at 40° C. then drowned onto ice (10 kg). The white precipitate was collected, redissolved in dichloromethane, washed with water, dried over magnesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 15 g. This solid was dissolved in p-dioxane (50 mls) and KF (10 g) and refluxed for three hours. After cooling to ambient the reaction mixture was drowned onto ice (400 g), extracted with dichloromethane (3×200 mls), dried over magnesium sulphate and evaporated to a brown oil. Yield 9 g.
EXAMPLE 175 Preparation of 4-(3-carboethoxy-5-nitrothien-2-ylazo)-N-(2-cyanoethyl)-N-(4-fluorosulphenylphenyl)ethylaniline
2-Amino-3-carboethoxy-5-nitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-(2-cyanoethyl)-N-(4-fluorosulphonyl phenylethyl)aniline (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 547 nm and gives good fastness to washing, light and heat.
The N-(2-cyanoethyl)-N-(4-fluorosulphonylphenylethyl)aniline was prepared as follows:
N-(2-cyanoethyl)aniline (0.01 mol), potassium carbonate (0.01 mol), DMF (50 cm3) and 4-fluorosulphonylphenylpropylbromide (0.0 mol) were stirred at 100° C. for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (25 g). No further purification was required.
The 4-fluorosulphonylphenylpropylbromide was prepared as follows:
Phenylethyl bromide (36.5 g) was dissolved in chloroform (500 mls) and chlorosulphonic acid (233 g) added dropwise. Stirred for 12 hours at ambient then drowned onto ice (10kg). The white precipitate was collected, redissolved in dichloromethane, washed with water, dried over magnesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 40.8 g. This solid was dissolved in p-dioxane (200 mls) and KF (24.7 g) and refluxed for three hours. After cooling to ambient the reaction mixture was drowned onto ice (700 g), extracted with dichloromethane (3×200 mls), dried over magnesium sulphate and evaporated to a brown oil. Yield 33.7 g.
EXAMPLE 176 Preparation of 4-(3,5-dinitrothien-2-ylazo)-N-ethyl-N-(4-fluorosulphonylphenyl)methyl aniline
2-Amino-3,5-dininrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-ethyl-N-(4-fluorosulphonylbenzyl)aniline (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 605 nm and gives good fastness to washing, light and heat.
EXAMPLE 177 Preparation of 4-(3,5-dinitrothien-2-ylazo)-N-ethyl-N-(4-fluorosulphonylphenyl)propyl aniline
2-Amino-3,5-dinitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-ethyl-N-(4-fluorosulphonylphenylpropyl)aniline (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 617 nm and gives good fastness to washing, light and heat.
EXAMPLE 178 Preparation of 4-(3,5-dinitrothien-2-ylazo-N-(2-cyanoethyl)-N-(4-fluorosulphonylphenyl)ethyl aniline
2-Amino-3,5-dinitrothiophene (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-(2-cyanoethyl), N-(4-fluorosulphonylphenylethyl) aniline (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered, washed with water and methanol and oven dried at 50° C. The dry dye has a λmax of 580 nm and gives good fastness to washing, light and heat.
The following examples of dyes of Formula ##STR23## were prepared using the procedure of Example 172, the fluorosulphonylphenylalkyl bromides were prepared as described in examples 172, 174 and 175 as appropriate.
__________________________________________________________________________
                                   λmax/                           
EG R.sub.7                                                                
          R.sub.6                                                         
                 R.sub.3                                                  
                      R.sub.1   n  nm                                     
__________________________________________________________________________
179                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --H    --H  --C.sub.2 H.sub.5                                   
                                3  593                                    
180                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --NHCOCH.sub.3                                                  
                 --H  --C.sub.2 H.sub.5                                   
                                3  605.5                                  
181                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --CH.sub.3                                                      
                 --H  --CH(CH.sub.3)CH.sub.2 CH.sub.3                     
                                3  614                                    
182                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --CH.sub.3                                                      
                 --OCH.sub.3                                              
                      --C.sub.4 H.sub.9                                   
                                3  636                                    
183                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --CH.sub.3                                                      
                 --OCH.sub.3                                              
                      --C.sub.2 H.sub.5                                   
                                3  631                                    
184                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --CH.sub.3                                                      
                 --OCH.sub.3                                              
                      --CH(CH.sub.3).sub.2                                
                                1  594                                    
185                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --CH.sub.3                                                      
                 --OCH.sub.3                                              
                      --C.sub.2 H.sub.5                                   
                                2  621.5                                  
186                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --CH.sub.3                                                      
                 --OCH.sub.3                                              
                      --H       2  595                                    
187                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --NHCOCH.sub.3                                                  
                 --OCH.sub.3                                              
                      --C.sub.2 H.sub.5                                   
                                1  641                                    
188                                                                       
   --COOC.sub.2 H.sub.5                                                   
          --H    --H  --C.sub.4 H.sub.9                                   
                                3  585                                    
189                                                                       
   --NO.sub.2                                                             
          --H    --H  --C.sub.4 H.sub.9                                   
                                3  637                                    
__________________________________________________________________________
EXAMPLE 190 Preparation of 4-(2,4-dinitrophenylazo)-3-acetamido-6-methoxy-N-secbutyl-N-(4-fluorosulphonylphenyl)methyl aniline
2,4-Dinitroaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N-(4-fluorosulphonylbenzyl)-N-secbutylamino)-4-methoxyacetanilide (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 575 nm and gives good fastness to washing, light and heat.
The 3-(N-(4-fluorosulphonylbenzyl)-N-sec-butylamino)-4-methoxyacetanilide was prepared as follows:
3-(N-sec-butyl)amino-4-methoxyacetanilide, potassium carbonate (0.01 mol), DMF (50 cm3) and 4-fluorosulphonylbenzyl bromide (0.2 mol) were stirred at 100° C. for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (22 g). No further purification was required.
EXAMPLE 191 Preparation of 4-(2,4-dinitro-6-bromophenylazo)-3-acetamido-6-methoxy-N-secbutyl-N-(4-fluorosulphonylphenyl)methyl aniline
2,4-Dinitro-6-bromoaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N-(4-fluorosulphonylbenzyl)-N-sec butylamino)-4methoxyacetanilide (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The dry dye has a λmax of 594 nm and gives good fastness to washing, light and heat.
EXAMPLE 192 Preparation of 4-(2,4-dinitro-6-cyanophenylazo)-3-acetamido-6-methoxy-N-secbutyl-N-(4-fluorosulphonylphenyl)methyl aniline
The dye from Example 191 (2.2 mmol) was dissolved in DMF (30 cm3) and CuCN (0.2 g) and stirred at 60° C. for 1 hour. The reaction mix was drowned onto ice and the precipitate filtered. The dried filter cake was slurried in dichloromethane, filtered and the filtrate evaporated to a solid dye with λmax of 642 nm.
EXAMPLE 193 Preparation of 4-(2,4-dinitro-6-chlorophenylazo)-3-methyl-6-methoxy-N-n-butyl-N-(4-fluorosulphonylphenyl)n-propyl aniline
The method of Example 191 was used except that 2,4-dinitro-6-chloroaniline (0.01 mol) was used in place of the 2,4-dinitro-6-bromoaniline and 3-(N-(4-fluorosulphonylphenyl)propyl-N-n-butyl-6-methoxy)toludine (0.01 mol) was used in place of the 3-(N-(4-fluorosulphonylbenzyl)-N-secbutyl-4-methoxyacetanlide. The dye has a λmax of 586.5 nm and gives good fastness to washing, light and heat.
EXAMPLE 194 Preparation of 4-(2,4-dinitrophenylazo)-3-methyl-N-ethyl-N-(4-(3-fluorosulphonylbenzoyloxyl)n-butyl)aniline
2,4-Dinitroaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the N-ethyl-N-hydroxybutyl-3-toluidine (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The hydroxy dye (5 mmol) was dissolved in chloroform (20 cm3), potassium carbonate (0.7 g) and m-(sulphonylfluoride) benzoyl chloride (1.2 g) and refluxed for 2 hours. The reaction mix was filtered and the filtrate evaporated to yield a solid violet dye which gives good fastness to washing, light and heat.
EXAMPLE 195 Preparation of 4-(2,4-dinitro-6-bromophenylazo)-3-acetamido-N-n-propyl-N-(3-fluorosulphonylbenzoyloxy)ethyl aniline
2,4-Dinitro-6-bromoaniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25 cm3), cooled to 0°-5° C. and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0°-5° C. The reaction mixture was stirred for 10 minutes at 0°-5° C. then added dropwise to a mixture of the 3-(N-propyl-N-hydroxyethyl)acetanilide (0.01 mol), methanol (50 cm3) and ice (50 g). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50° C. The hydroxy dye (5 mmol) was dissolved in chloroform (20 cm3), potassium carbonate (0.7 g) and m-(sulphonylfluoride) benzoyl chloride (1.2 g) and refluxed for 2 hours. The reaction mix was filtered and the filtrate evaporated to yield a solid dye (λmax 552 nm) which gives good fastness to washing, light and heat.
EXAMPLE 196 Preparation of 4-(2-chloro-5-fluorosulphonylphenylazo)-N-ethyl-N-benzyl aniline
3-Amino-4-chloro benzene sulphonyl fluoride (2 parts) was stirred in acetic/propionic acid 86/14 vol/vol (25 parts) and cooled to 0°-5° C. Nitrosyl sulphuric acid solution (3.8 parts) was added dropwise at 0°-5° C. and stirred under these conditions for 2 hours. The diazo solution was then added to a mixture of N-ethyl-N-benzyl aniline (2.7 parts), methanol (100 parts) and sulphamic acid (1 part) stirring at 0°-5° C. After stirring under these conditions for 30 mins, ice/water (100 parts) was added and the mixture stirred for a further 1 hour. The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts) and refiltered. Dried at 50° C. to yield 4-(2-chloro-5-fluorosulphonylphenylazo)-N-ethyl-N-benzyl aniline (2.3 parts).
When applied to polyester materials from an aqueous dispersion, the dye gave yellow shades. λmax 463 nm.
The following examples of dyes of Formula ##STR24## were prepared by the procedure of Example 196
__________________________________________________________________________
Example                                                                   
      R.sup.1  R.sup.2    R.sup.4                                         
                                 λmax/nm                           
__________________________________________________________________________
197   --C.sub.2 H.sub.4 CN                                                
               --C.sub.2 H.sub.4 CN                                       
                          --H    421                                      
198   --C.sub.2 H.sub.4 CN                                                
               --C.sub.2 H.sub.4 COOCH.sub.2 CN                           
                          --H    429                                      
199   --C.sub.2 H.sub.4 CN                                                
               --C.sub.2 H.sub.4 CN                                       
                          --CH.sub.3                                      
                                 429                                      
200   --C.sub.2 H.sub.4 CN                                                
               --C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                       
                          --NHCOCH.sub.3                                  
                                 466                                      
201   --C.sub.2 H.sub.4 OCOCH.sub.3                                       
               --C.sub.2 H.sub.4 OCOCH.sub.3                              
                          --NHCOCH.sub.3                                  
                                 473                                      
202   --C.sub.2 H.sub.5                                                   
               --C.sub.2 H.sub.4 CN                                       
                          --H    442                                      
203   --C.sub.2 H.sub.5                                                   
               --C.sub.2 H.sub.4 CN                                       
                          --CH.sub.3                                      
                                 449                                      
204   --C.sub.4 H.sub.9                                                   
               --C.sub.2 H.sub.4 CN                                       
                          --H    444                                      
205   --C.sub.4 H.sub.8 OCOCH.sub.3                                       
               --C.sub.4 H.sub.8 OCOCH.sub.3                              
                          --CH.sub.3                                      
                                 477                                      
206   --C.sub.2 H.sub.5                                                   
               --CH.sub.2 phenyl                                          
                          --CH.sub.3                                      
                                 469                                      
__________________________________________________________________________
EXAMPLE 207 Preparation of 4-(2-chloro-4-fluorosulphonylphenylazo)-N-ethyl-N-benzyl aniline
3-Chloro-4-amino benzene sulphonylfluoride (1 part) was stirred in acetic/propionic acid 86/14 vol/vol (15 parts) and cooled to -5° C. Nitrosyl sulphuric acid solution (1.9 parts) was added dropwise then stirred at 0°-5° C. for 2 hours. The diazo solution was then added to a stirred mixture of N-ethyl-N-benzyl aniline (2.0 parts), methanol (50 parts), sulphamic acid (0.5 parts) and sodium acetate (5 parts) with ice/water (100 parts) at 0°-5° C. After stirring under these conditions for 1 hour, the dye was filtered off and washed well with water. The damp solid was slurried in methanol (100 parts) and re-filtered. Dried at 50° C. to yield the product 4-(2-chloro-4-fluorosulphonyl phenylazo)-N-ethyl-N-benzyl aniline (1.5 parts). When applied to polyester materials from an aqueous dispersion the dye gave orange shades. λmax 483 nm
EXAMPLE 208 Preparation of 4-(2-chloro-4-fluorosulphonylphenylazo)-3-acetamido-N-N-bis(2-acetoxyethyl)aniline
The procedure of Example 207 was repeated except that in place of 2 parts of N-ethyl-N-benzyl aniline; 2 parts of N,N-bis(2-acetoxyethyl)aminoacetanilide were used to yield the product, 4-(2-chloro-4-fluorosulphonylphenylazo)-3-acetamido-N,N-bis(2-acetoxyethyl)aniline (1.2 parts). When applied to polyester materials from an aqueous dispersion, the dye gave orange shades. λmax 494 nm.
EXAMPLE 209 Preparation of 4-(2-methoxy-5-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-benzylaniline
3-Amino-4-methoxy benzene sulphonylfluoride (1 part) was stirred in acetic/propionic acid 86/14 vol/vol (15 parts) and cooled to 0°-5° C. Nitrosyl sulphuric acid solution (1.9 parts) was dropwise and stirred at 0°-5° C. for 2 hours. The diazo solution was then added to a stirred mixture of N-ethyl-N-benzyl-m-toluidine (1.3 parts), methanol (50 parts), sulphamic acid (0.5 parts) and sodium acetate (5 parts) stirring in ice/water at 0°-5° C. After stirring for 2 hours under these conditions, the dye was filtered off and washed well with water. The damp solid was slurried in water and re-filtered. The dye was then stirred in methanol at room temperature for 1 hour, filtered, and dried at 50° C. to yield the product, 4-(2-methoxy-5-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-benzyl aniline (1.5 parts). When applied to polyester materials from an aqueous dispersion, the dye gave yellow shades. λmax 450.
The following examples of dyes of Formula ##STR25## were prepared by the procedure of Example 209
______________________________________                                    
Example                                                                   
       R.sup.1     R.sup.2     R.sup.4                                    
                                      λmax/nm                      
______________________________________                                    
210    --C.sub.4 H.sub.8 OCOCH.sub.3                                      
                   --C.sub.4 H.sub.8 OCOCH.sub.3                          
                               --CH.sub.3                                 
                                      455                                 
211    --C.sub.2 H.sub.5                                                  
                   --C.sub.2 H.sub.4 CN                                   
                               --H    449                                 
212    --C.sub.2 H.sub.5                                                  
                   --H         --CH.sub.3                                 
                                      429                                 
213    --C.sub.2 H.sub.5                                                  
                   --CH.sub.2 phenyl                                      
                               --H    444                                 
______________________________________
EXAMPLE 214 Preparation of 4-(4-chloro-5-fluorosulphonylphenylazo)-N,N-bis(2-cyanoethyl)aniline
i) 2--Chloro-5-nitro benzene sulphonic acid (484 parts) was charged to a flask then quickly added thionyl chloride (1190 parts) and dimethyl formamide (12 parts). The resultant slurry was heated to 60° C. and stirred at 60°-65° C. for a total of 5 hours. The mixture was cooled to room temperature then poured onto ice/water. The precipitated solid was filtered off and washed with cold water before drying in vac oven to yield the product 2-chloro-5-nitro benzene sulphonylchloride (395 parts).
ii) 2--Chloro-5-nitro benzene sulphonylchloride (40 parts) was stirred in p-dioxane (48 parts) at room temperature. Potassium fluoride (10 parts) dissolved in water (35 parts) was added, and the mixture heated to 70° C. Stirred at 70° C. for 4 hours then cooled to room temperature and poured onto ice/water. Allowed to stand for 2 days then filtered off the precipitate and dried in air to yield the product 2-chloro-5-nitro benzene sulphonylfluoride (36 parts).
iii) The 2-chloro-5-nitro benzene sulphonylfluoride (2.4 parts) was stirred. in glacial acetic acid (25 parts) with iron powder (2 parts). Heated to reflux and stirred at reflux for 2.5 hours, then cooled to room temperature, poured onto ice/water and allowed to stand at room temperature overnight. The resultant precipitate was filtered off and dried in air to yield the product 2-chloro-5-amino benzene sulphonylfluoride (0.8 parts).
iv) 2-Chloro-5-amino benzene sulphonylfluoride (2.1 parts) was stirred in acetic/propionic acid 86/14 vol/vol (25 parts) and cooled to 0°-5° C. Nitrosyl sulphuric acid solution (3.8 parts) was added and stirred at 0°-5° C. for 3 hours. The diazo solution was then added to a mixture of N,N-bis(2-cyanoethyl)aniline (2.1 parts), methanol (75 parts) and sulphamic acid (1 part) stirring in ice/water (75 parts) at 0°-5° C. Stirred under these conditions for 1 hour then allowed to stand at room temperature overnight before filtering off the dye. The solid was dried overnight to yield the product 4-(4-chloro-5-fluorosulphonylphenylazo)-N,N-bis(2-cyanoethyl)aniline (3.6 parts). The dye, when applied to polyester material from an aqueous dispersion, gave yellow shades. λmax 414 nm.
The following Examples of dyes of Formula ##STR26## were prepared by the procedure of Example 214
______________________________________                                    
Ex-                                     λ                          
am-                                     max/                              
ple  R.sup.1     R.sup.2       R.sup.4  nm                                
______________________________________                                    
215  --C.sub.2 H.sub.4 OCOCH.sub.3                                        
                 --C.sub.2 H.sub.4 OCOCH.sub.3                            
                               --NHCOCH.sub.3                             
                                        476                               
216  --C.sub.2 H.sub.4 CN                                                 
                 --C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                     
                               --NHCOCH.sub.3                             
                                        466                               
217  --C.sub.2 H.sub.4 CN                                                 
                 --C.sub.2 H.sub.4 CN                                     
                               --CH.sub.3                                 
                                        421                               
218  --C.sub.2 H.sub.5                                                    
                 --CH.sub.2 phenyl                                        
                               --H      459                               
219  --C.sub.2 H.sub.4 CN                                                 
                 --C.sub.2 H.sub.4 COOCH.sub.2 CN                         
                               --H      421                               
______________________________________
EXAMPLE 220 Preparation of 4-(3-nitro-5-fluorosulphonylthien-2-ylazo)-3-acetamido-N,N-diethylamino)aniline
i) 2--Chlorosulphonyl-5-chlorothiophene (19.8 parts) was added to fuming nitric acid (80 parts), allowing to exotherm to 35° C. Heated to 50° C. and stirred under these conditions for 2 hours. Cooled to room temperature then poured onto ice/water with vigorous stirring. The white solid was filtered off and dried to yield the product 2-chlorosulphonyl-4-nitro-5-chlorothiophene (19 parts).
ii) 2--Chlorosulphonyl-4-nitro-5-chlorothiophene (20.1 parts) were stirred in p-dioxane (80 parts) at room temperature. Potassium fluoride (5.2 parts) in water (20 parts) was added and the mixture heated to 50° C. Stirred under these conditions for 4 hours, then cooled and poured onto ice/water. Ethyl acetate was then added to extract the product and separated. Dried over magnessium sulphate then screened and concentrated to yield the product 2-fluorosulphonyl-4-nitro-5-chloro thiophene (20.4 parts).
iii) The 2-fluorosulphonyl-4-nitro-5-chlorothiophene (20.4 parts), was added to methanol (240 parts) with hexamine (22.5 parts). Heated to reflux and stirred under these conditions for 4 hours. Cooled to room temperature and poured onto 10% sulphuric acid solution (250 parts). The product was extracted out with ethyl acetate, separated and dried over magnessium sulphate, then screened and concentrated to yield the product 2-fluorosulphonyl-4-nitro-2-aminothiophene (16 parts).
iv) 2-Fluorosulphonyl-4-nitro-5-aminothiophene (4.2 parts) was added over 30 mins to a stirred solution of acetic/propionic acid 86/14 vol/vol (60 parts) with nitrosyl sulphuric acid solution (10 parts) at 0°-5° C. Stirred under these conditions for 4 hours. The diazo solution was then added to a mixture of 3-N,N-diethyl aminoacetanilide (4.2 parts), water (40 parts), methanol (15 parts), and sulphamic acid (1 part) stirring in 50% sulphuric acid solution at 0°-5° C. Stirred under these conditions for 45 mins then filtered off the dye and washed well with water. Dried in the oven overnight to yield the product 4-(3-nitro-5-fluorosulphonylthien-2-ylazo)-3-acetamido-N,N-(diethylamino)aniline (0.6 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades. λmax 615 nm.
EXAMPLE 221 Preparation of 4-(3-nitro-5-fluorosulphonylthien-2-ylazo)-3-methyl-N-N-diethylaminoanilin
The procedure of Example 220iv) was repeated except that in place of the 3-N,N-diethylaminoacetanilide 0.4 parts of 3-methyl-N,N-diethylaminoaniline was used to yield 4-(3-nitro-5-fluorosulphonylthien-2ylazo)-3-methyl-N,N-diethylaminoaniline (0.3 parts). When applied to polyester materials from an aqueous dispersion the dye gave blue shades. λmax 629 nm.
General Method for the Preparation of Dye Examples 222-238
i) Preparation of 2-nitro-4-fluorosulphonylaniline
N-acetyl sulphanilyl chloride (100 g) was dissolved in concentrated sulphuric acid (515 cm3), cooled to 4° C. and a mixture of concentrated nitric acid (38.6 cm3) and concentrated sulphuric acid (42.9 cm3) added dropwise maintaining the temperature at 4°-6° C. After hour the reaction mix was drowned onto ice and the precipitate collected, extracted into dichloromethane and evaporated to a yellow solid (92 g). 31 g of this yellow solid was refluxed for 3 hours in water (20 cm3), p-dioxane (20 cm3) and KF (19.4 g). then drowned onto ice and the precipitate collected. This precipitate was refluxed in absolute ethanol (35 cm3) and concentrated hydrochloric acid (35 cm3) for 1 hour then drowned onto ice, filtered and suction dried. Recrystallisation from ethanol yielded 8.7 g of the required compound.
ii) Preparation of 2-nitro-4-fluorosulphonyl-6-chloroaniline
2-Nitro-5-chloracetanilide (10 g) was added cautiously to chlorosulphonic acid (40 cm3) then heated at 120° C. for 2 hours. The reaction mix was cooled to 50° C. and drowned onto ice. The precipitate was filtered, washed with a little water and suction dried. This solid was dispersed in water (20 cm3), p-dioxane (20 cm3) and KF (10 g). After refluxing for 2 hours the reaction mix was drowned into water, the precipitate filtered and suction dried. This solid was refluxed in water (50 cm3) and 36% HCl (50 cm3) for 1 hour, drowned onto ice and the precipitate collected. Yield 3.5 g. 2-Nitro-4-fluorosulphonylaniline (0.01 mol) (for dyes 222-230) or 2-nitro-6-chloro-4-fluorosulphonyl-aniline (0.01 mol) (for dyes 231-238) was dispersed in a mixture of acetic:propionic acid (86:141 (25ml) and cooled to 0°-5° C. and nitrosylsulphuric acid (0.01 mol) was then added portionwise at 0°-5° C. The reaction mixture was stirred for 10 min. at 0°-5° C. and then added dropwise to a mixture of the required coupler (0.01 mol), methanol (50 ml) and ice (50 g) maintaining the acidity between pH3 and pH5 by addition of sodium acetate. The resultant precipitate was filtered, washed with water and then methanol 1:1 water and dried in air. The dry dye, when applied to polyester as an aqueous dispersion, gave good fastness to washing, light and heat.
(i) Preparation of Couplers for Dye Examples 222-224, 226, 229 and 231-235 Method 1
Dye Examples 222-224, 226, 229 and 231-235 were prepared from the appropriate N,N-dialkyl-(3-ethylsuccinamido-6-methoxy)aniline coupling components which were prepared according to the following method. A mixture of 3-(N,N-dialkyl)-4-methoxyaniline (0.01 mol), ethylsuccinyl chloride (0.01 mol) and pyridine (0.01 mol) in dichloromethane (50 ml) was stirred and heated under gentle reflux for 4 h and then allowed to cool and was then drowned out into water. The resulting product was extracted into dichloromethane, dried (MgSO4) and evaporated to dryness in vacuo to yield the required Coupler as a brown oil.
(ii) Preparation of Couplers for Dye Examples 225, 227, 228, 230 and 236-238--Method 2
Dye Examples 225, 227, 228, 230 and 236-238 were prepared from the appropriate N,N-dialkyl-(3-ethylsuccinamido-6-methoxy)aniline coupling components which were prepared according to the following method. A mixture of 3-(N,N-dialkylamino)-4-methoxyaniline (0.01 mol) and succinic anhydride (0.01 mol) in anhydrous toluene (50 ml) was stirred for 1.5 h and then evaporated to dryness in vacuo to give a brown gum. The brown gum (the carboxylic acid intermediate) was esterified by treatment with an appropriate alcohol (0.1 mol) and conc. sulphuric acid (1 ml) at 100° C. for 1 h and was then allowed to cool. The mixture was drowned out into water and the product was extracted into ethyl acetate, dried (MgSO4) and evaporated to dryness in vacuo to yield the required coupler as a brown oil.
Dye Examples 222-238 are summarised below
__________________________________________________________________________
 ##STR27##                                                                
Exam-                                                                     
ple R.sup.14                                                              
       R.sup.1                                                            
           R.sup.2   R.sup.22      max/nm                                 
__________________________________________________________________________
222 H  C.sub.3 H.sub.7                                                    
           C.sub.3 H.sub.7                                                
                     C.sub.2 H.sub.5                                      
                                   592                                    
223 H  C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     C.sub.2 H.sub.5                                      
                                   590                                    
224 H  C.sub.4 H.sub.9                                                    
           C.sub.4 H.sub.9                                                
                     C.sub.2 H.sub.5                                      
                                   594                                    
225 H  C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     C.sub.4 H.sub.9                                      
                                   591                                    
226 H  C.sub.2 H.sub.5                                                    
           CH.sub.2 phenyl                                                
                     C.sub.2 H.sub.5                                      
                                   585                                    
227 H  C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     CH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2              
                                   590                                    
228 H  C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     CH.sub.2 phenyl                                      
                                   591                                    
229 H  C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.4 phenyl                                         
                     C.sub.2 H.sub.5                                      
                                   588                                    
230 H  C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     CH.sub.2 (tetrahydrofuran-2-yl)                      
                                   590                                    
231 Cl C.sub.3 H.sub.7                                                    
           C.sub.3 H.sub.7                                                
                     C.sub.2 H.sub.5                                      
                                   609                                    
232 Cl C.sub.2 H.sub.5                                                    
           CH.sub.2 phenyl                                                
                     C.sub.2 H.sub.5                                      
                                   601                                    
233 Cl C.sub.4 H.sub.9                                                    
           C.sub.4 H.sub.9                                                
                     C.sub.2 H.sub.5                                      
                                   610                                    
234 Cl C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     C.sub.2 H.sub.5                                      
                                   607                                    
235 Cl C.sub.2 H.sub.5                                                    
           CH(CH.sub.3)CH.sub.2 CH.sub.3                                  
                     C.sub.2 H.sub.5                                      
                                   606                                    
236 Cl C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     C.sub.4 H.sub.9                                      
                                   607                                    
237 Cl C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     CH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2              
                                   607                                    
238 Cl C.sub.2 H.sub.5                                                    
           C.sub.2 H.sub.5                                                
                     CH.sub.2 phenyl                                      
                                   607                                    
__________________________________________________________________________
Preparation of Dye Examples 239-246
Dye Examples 239-246 were prepared using the same general method as was used for the preparation of dye examples 222-238. The dyes, when applied to polyester as aqueous dispersions, gave good fastness to washing light and heat.
The couplers for dye Examples 239, 240 and 246 were prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method using acetylsalicoyl chloride (0.01 mol) in place of ethylsuccinyl chloride.
The coupler for dye Example 241 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using butylchloroformate (0.01 mol) in place of ethylsuccinyl chloride. The coupler for dye Example 242 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using ethylmalonyl chloride (0.01 mol) in place of ethylsuccinyl chloride.
The coupler for dye Example 243 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 2 using maleic anhydride (0.01 mol) in place of succinic anhydride and ethanol as the esterifying alcohol.
The coupler for dye Example 244 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 2 using 2,2-dimethylsuccinic anhydride (0.01 mol) in place of succinic anhydride and ethanol as the esterifying alcohol.
The coupler for dye Example 245 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using 4-methoxycarbonylphenylchloroformate (0.01 mol) in place of ethylsuccinyl chloride.
Dye Examples 239-246 are summarised below
______________________________________                                    
 ##STR28##                                                                
Example                                                                   
       R.sup.14                                                           
              R.sup.23        1.sub.max /nm                               
______________________________________                                    
239    H      2-OCOCH.sub.3 phenyl                                        
                              598                                         
240    H      2-OHphenyl      590                                         
241    H      OC.sub.4 H.sub.9                                            
                              587                                         
242    H      CH.sub.2 COOC.sub.2 H.sub.5                                 
                              591                                         
243    H      CHCHCOOC.sub.2 H.sub.5                                      
                              596                                         
244    H      CH.sub.2 C(CH.sub.3).sub.2 COOC.sub.2 H.sub.5               
                              592                                         
245    H      4-COOCH.sub.3 phenyl                                        
                              573                                         
246    Cl     4-OCOCH.sub.3 phenyl                                        
                              601                                         
______________________________________
EXAMPLE 247 Preparation of 5-(2,5-dichloro-4-fluorosulphonylphenylazo)-4,6-diaminopropylthiopyrimidin
The procedure of Example 1 was repeated except that in place of the 1.6 parts of N,N-bis-(2-cyanoethyl)aniline; 1.5 parts of 4,6-diamino-2-propylthiopyrimidine were used. The product, 5-(2,5-dichloro-4-fluorosulphonylphenylazo)-4,6-diaminopropylthiopyrimidine (3.4 parts) λmax=420 nm, when applied to polyester materials from an aqueous dispersion gives bright yellow shades with excellent fastness to light and wet treatments.
EXAMPLE 248 Preparation of 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-chloro-N-ethyl-N-methylphthalimidoaniline
The procedure of Example 1 was repeated except that in place of the 1.6 parts of N,N-bis-(2-cyanoethyl)aniline; 2.6 parts of 3-chloro-N-ethyl,N-methylphthalimidoaniline were used. The product, 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-chloro-N-ethyl, N-methylphthalimidoaniline (4.0 parts) λmax=455 nm, when applied to polyester materials from an aqueous dispersion gives orange shades with excellent fastness to light and wet treatments.
EXAMPLE 249 Preparation of 4-(2f5-dichloro-4-fluorosulphonylphenylazo)-3-methylmorpholinobenzene
The procedure of Example 1 was repeated except that in place of the 1.6 parts of N,N-bis-(2-cyanoethyl)aniline; 1.5 parts of 3-methylmorpholinobenzene were used. The product, 4-(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methylmorpholinobenzene (1.9 parts) λmax=480 nm, when applied to polyester materials from an aqueous dispersion gives dull bluish red shades with excellent fastness to light and wet treatments.
EXAMPLE 250 Preparation of 4-(2-nitro-4-fluorosulphonyl-6-chlorophenylazo)-1-(N-ethylamino)naphthalene
The procedure of Example 139 was used expect that 1-(N-ethylamino)naphthalene (7.86 nmol) was used in place of the 3-(N,N-diethylamino)acetanilide. The dye has a λmax of 571 nm.
EXAMPLE 251 Preparation of 4-(2-nitro-4-fluorosulphonyl-6-chlorophenylazo)-1-(N-ethyl-N-n-propylamino)naphthalene
The procedure of Example 139 was used except that 1-(N-ethyl-N-n-proylamino)naphthalene was used in place of the 3-(N,N-diethylamino)acetanilide. The dye has a λmax of 578 nm.
EXAMPLE 252 Preparation of 4-(4,8-difluorosulphonylnaphth-2-ylazo)N-N-diethylaniline
To a mixture of 2-amino-4,8difluorosulphonylnaphthalene (1.6 parts) and acetic/propionic acid mixture (20 parts, 86/14 vol/vol), stirring at 0.5° C., was added dropwise nitrosyl sulphuric acid soln (1.5 parts). The mixture was stirred at this temperature,for a further 15 mins.
The diazo solution was added to a mixture of N,N-diethylaniline (0.9 parts), methanol (50 parts) and sulphamic acid (0.5 parts); stirring at 0.5° C. After stirring for 2 hours at this temperature, the product was isolated by filtration, washed with water and dried at 50° C. to yield; 4-(4,8-difluorosulphonylnaphthyl-2-azo)-N,N-diethylaniline (1.6 parts). When applied to polyester materials from an aqueous dispersion, the dye gives red shades with excellent fastness to wet treatments. λmax of 500 nm.
The following Examples of dyes of Formula
______________________________________                                    
 ##STR29##                                                                
were prepared by the procedure of Example 252:                            
Example R.sup.1   R.sup.2    R.sup.4  λmax                         
______________________________________                                    
253     C.sub.4 H.sub.9                                                   
                  C.sub.4 H.sub.9                                         
                             H        509                                 
254     C.sub.2 H.sub.5                                                   
                  C.sub.2 H.sub.5                                         
                             CH.sub.3 519                                 
255     C.sub.2 H.sub.5                                                   
                  C.sub.2 H.sub.5                                         
                             NHCOCH.sub.3                                 
                                      530                                 
256     C.sub.2 H.sub.4 CN                                                
                  C.sub.2 H.sub.4 CN                                      
                             H        460                                 
______________________________________
EXAMPLE 257 Preparation of 4-(2-cyan-4-nitrophenylazo)-N-ethyl-N-2-(4-fluorosulphonylphenoxy)ethylaniline
To a mixture of 2-cyano-4-nitroaniline (1.5 parts) and acetic/propionic acid mixture (10 parts, 86/14 vol/vol), stirring at 0.5° C., was added dropwise nitrosyl sulphuric acid soln (2.0 parts). The mixture was stirred at this temperature for a further 30 mins.
The diazo solution was added to a mixture of N-ethyl,N-2-(4-fluorosulphonylphenoxyl)-ethylaniline (3.0 parts), methanol (50 parts) and sulphamic acid (0.5 parts); stirring at 0.5° C. After stirring for 2 hours at this temperature, the product was isolated by filtration, washed with water and dried at 50° C. to yield; 4-(2-cyano-4-nitrophenylazo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (3.0 parts). When applied to polyester materials from an aqueous dispersion, the dye gives bluish red shades with excellent light fastness and excellent fastness to wet treatments. λmax of 530 nm.
EXAMPLE 258 Preparation of 4-(3-acetyl-5-nitrothien-2-ylazo)-N-ethyl-N-2-(4-fluorosulphonylphenyoxy)ethylaniline
The procedure of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.7 parts of 2-amino-3-acetyl-5-notrothiophene were used. The product 4-(3-acetyl-5-nitrothienyl-2-azo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (2.0 parts) when applied to polyester materials from an aqueous dispersion gives reddish blue shades with excellent fastness to light and wet treatments. λmax of 590 nm.
EXAMPLE 259 Preparation of 4-(2-chloro-4-nitrophenylazo)-3-methyl-N-ethyl-N-2-fluorosulphonylphenoxy)ethylaniline
To chlorosulphonic acid (17.5 parts) stirring at 0.5° C., was added gradually 3 -methyl -4 -(2 -chloro-4 -nitrophenylazo)-N-ethyl, N-2-phenoxyethylaniline (8.0 parts). Thionyl chloride (5.4 parts) was added and the mixture was stirred at 0.5° C. for 2 hours. The reaction mixture was drowned into ice/water (500 parts), the product was isolated by filtration and washed acid-free with cold water.
The filter cake was set stirring with 1,4-dioxan (40 parts) and a solution of potassium fluoride (1.8 parts) in water (1.0 parts) was added. The mixture was heated at 60° C. for 3 hours, cooled to ambient and the product was isolated by filtration to yield; 3-methyl-4-(2-chloro-4-nitrophenylazo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (4.5 parts).
The product when applied to polyester materials from an aqueous dispersion gives mid red shades with excellent fastness to light and wet treatments. λmax of 510 nm.
EXAMPLE 260 Preparation of 4-(6-thiocyanatobenzothiazol-2-ylazo)-N-ethyl-N-2-(4-fluorosulphonylphenoxy)ethylanaline
The procedure of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.9 parts of 2-amino-6-thiocyanatobenzthiazole were used.
The product, 4-(6-thiocyanatobenzthiazolyl-2-azo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (1.4 parts) When applied to polyester materials from an aqueous dispersion gives bluish red shades with excellent fastness to light and wet treatments. λmax of 522 nm.
EXAMPLE 261 Preparation of 4-(2,6-dichloro-4-nitrophenylazo)-N-ethyl-N-2-(4-fluorosulphonylphenoxy)ethylaniline
The procedure of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.9 parts of 2-amino-6-thiocyanatobenzthiazole were used.
The product, 4-(6-thiocyanatobenzthiazolyl-2-azo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (1.4 parts) when applied to polyester materials from an aqueous dispersion gives bluish red shade with excellent fastness to light and wet treatments. λmax of 522 nm.
EXAMPLE 262 Preparation of 4-(6-thiocyanatobenzothiazol-2-ylazo)-3-N-ethyl-N-2-(4-fluorosulphonylphenoxy)ethylaniline
The procedure of Example 257 was repeated except that in place of the 3.0 parts of N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline, 3.1 parts of N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethyl-m-toluidine were used.
The product, 3-methyl-4-(6-thiocyanatobenzthiazolyl-2-azo)-N-ethyl,N-2-(4-fluorosulphonylphenoxy)ethylaniline (1.7 parts) when applied to polyester materials from an aqueous dispersion gives violet shades with excellent fastness to light and wet treatments. λmax of 540 nm.
EXAMPLES 263 AND 264
Dyes prepared by the procedure described for Example 139 but using the 1-naphthylamino in place of 3-(N,N-diethylamino)acetanilide are of Formula:
______________________________________                                    
 ##STR30##                                                                
Example   R.sub.1       R.sub.2                                           
                               .sub.max /nm                               
______________________________________                                    
263       C.sub.2 H.sub.5                                                 
                        H      571                                        
264       C.sub.2 H.sub.5                                                 
                        C.sub.3 H.sub.7                                   
                               578                                        
______________________________________
EXAMPLE 265 Preparation of 1-n-butyl-5(2,5-dichloro-4-fluorosulphonylphenylazo)-3-cyano-6-hydroxy-4-methyl-2-oxo-IH-pyridine
The procedure of Example 1 was repeated except that in place of the 3.0 g of 3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline., 1.8 g of 1-n-butyl-3-cyano-6-hydroxy-4-methyl-2-oxo-IH-pyridine were used. The product 1-n-butyl-5(2,5-dichloro-4-fluorosulphonylphenylazo).-3-cyano-6-hydroxy-4-methyl-2-oxo-IH-pyridine (2.5 g) when applied to polyester materials from aqueous dispersion gives greenish yellow shades with excellent wet and light fastness properties. λmax=435 nm.
EXAMPLE 266 Preparation of 1-phenyl-3-t-butyl-5-amino-4-(2,5-dichloro-4-fluorosulphonylphenylazo)pyrazole
The procedure of Example 1 was repeated except that in place of the 3.0 g of 3-methyl-N-ethyl-N-(2-benzoyloxyethyl)aniline,. 1.5 g of 1-phenyl-3-t-butyl-5-aminopyrazole were used. The product 1-phenyl-3-t-butyl-5-amino-4-(2,5-dichloro-4-fluorosulphonylphenylazo)pyrazole (2.1 g) when applied to polyester materials form aqueous dispersion gives greenish yellow shades with excellent wet and light fastness properties. λmax=442 nm.
EXAMPLES 267-278
The dyes of the following formulae may be made by the procedure of Example 1 by diazotising the appropriate amino and coupling onto the appropriate coupling component
EXAMPLE 267 ##STR31## EXAMPLE 268 ##STR32## EXAMPLE 269 ##STR33## EXAMPLE 270 ##STR34## EXAMPLE 271 ##STR35## EXAMPLE 272 ##STR36## EXAMPLE 273 ##STR37## EXAMPLE 274 ##STR38## EXAMPLE 275 ##STR39## EXAMPLE 276 ##STR40## EXAMPLE 277 ##STR41## EXAMPLE 278 ##STR42##

Claims (22)

I claim:
1. A compound which is free from water solubilising groups of Formula (1):
A--N═N--D                                              Formula (1)
wherein
A and D each independently is a heterocyclic or carbocyclic group, which is unsubstituted or is substituted by one or more substituents selected from the group consisting of cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl, --OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHCOaryl, --NHSO2 alkyl, --NHSO2 aryl, --Salkyl, --Saryl, --SO2 alkyl, --SO2 aryl, --SCN, --NR1 R2 in which R1 and R2 each independently is --H, alkyl, aryl or cycloalkyl, and groups of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or --NR20 --Z-- or --O--Z-- in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCOR21, --OH or --CN in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or substituted or unsubstituted alkyl, each of the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 being unsubstituted or substituted by one or more of --OH, --CN, --F, --Cl, --Br, --I, --SO2 F, alkoxy, alkenyl, phenyl, phenylSO2 F, aryloxy, aryloxySO2 F, --N(alkyl)2, --OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, --COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO2 F, --OCOphenylNO2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, --OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkylOalkyl, --COOalkylOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, --OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, --OalkylCOOalkylCOOalkyl, --OalkylOCOalkylOalkyl, --COOalkylOCOalkyl or --COOalkylCOOalkyl, ##STR43## in which L is --H or alkyl, at least one of A or D being substituted by at least one --SO2 F group or is substituted by at least one substituent which is itself substituted by at least one --SO2 F group, and
at least one of A or D is substituted by at least one ester group or is substituted by at least one substituent which is itself substituted by at least one ester group, provided that one of A1 or D1 is not ##STR44## and except for the compound 4-(4-fluorosulphonylphenylazo)-N-ethyl-N-acetoxyethylaniline.
2. A compound according to claim 1 in which the compound of Formula (1) is of Formula (3): ##STR45## wherein R1 and R2 each independently is --H, substituted or unsubstituted C1-6 -alkyl or substituted or unsubstituted aryl;
R3, R4, R5 and R6 each independently is --H, --F, --Cl, --Br, --I, --SO2 F or substituted or unsubstituted C1-6 -alkyl, C1-6 -alkoxy, C1-6 alkanoylamino, --NHSO2 alkyl or phenoxy;
R7, R8 and R9 each independently is --H, C1-6 -alkyl, --NO2, --COOC1-6 -alkyl, --OCOalkyl, --Cl, --F, --Br, --I, --COC1-6 -alkyl, --CN, formyl, protected formyl or --SO2 F, provided that at least one of R1 to R9 is --SO2 F or is a substituent which is itself substituted by at least one --SO2 F group, and provided that R7 and R9 are not both --SO2 F.
3. A compound according to claim 1 in which A and D each independently is selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4- and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, phenyl and naphthyl.
4. A compound according to claim 1 in which A and D each independently is selected from thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl, quinolinyl.
5. A compound according to claim 1 in which A and D each independently is selected from thien-2-yl, phenyl, naphth-1-yl, naphth-2-yl, thiazol-2-yl, isothiazol-5-yl, pyrid-4-one-5-yl or quinolinyl.
6. A compound according to claim 1 in which A is thien-2-yl or phenyl and D is phenyl or naphth-1-yl.
7. A compound according to claim 1 in which the compound of Formula (1) is of Formula (4): ##STR46## wherein R1 and R2 each independently is --H, substituted or unsubstituted C1-6 -alkyl or substituted or unsubstituted aryl;
R3, R4, R5 and R6 each independently is --H, --F, --Cl, --Br, --I, --O2 F or substituted or unsubstituted C1-6 alkyl, C1-6 -alkoxy, C1-4 -alkanoylamino, --NHSO2 alkyl or -phenoxy; and
R10 to R14 each independently is --H, alkoxy, alkyl, --NO2, --SO2 F, --F, --Cl, --Br, --I or --CN; provided that when R10 is SO2 F, R12 is not --NO2 and R11, R13 and R14 are not all --H.
8. A compound according to claim 1 in which the compound of Formula (1) is of Formula (7): ##STR47## in which R1 and R2 each independently is substituted or unsubstituted C1-6 -alkyl;
R4 is alkyl or a group of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, --NR20 --Z--, --COOZ or --O--Z in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl or a direct link and
R20 is --H, alkyl, aryl or alkylaryl,
W is --CO2 R21, --OCOR21 or --OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or alkyl;
R5 is --H, C1-6 -alkoxy or phenoxy;
R10 is --NO2 or --Cl; and
R13 and R14 each independently is --H or --Cl.
9. A compound according to claim 1 in which the compound of Formula (1) is of Formula (5): ##STR48## wherein R1 and R2 each independently is --H or substituted or unsubstituted C1-6 -alkyl;
R3 is substituted or unsubstituted C1-6 -alkyl or C1-6 -alkoxy;
R4 is substituted or unsubstituted C1-6 -alkyl or C1-6 -alkoxy;
R10 is substituted or unsubstituted C1-6 -alkyl, NO2 or Cl;
R15 to R18 each independently is --H, --C1-6 -alkyl, --C1-6 -alkoxy, --F, --Cl, --Br, --I, --SO2 F, --NO2, --CN or --NR1 R2 ;
R12 is --NO2 or --SO2 F;
R11 is --H; and
R13 and R14 each independently is --H or --Cl.
10. A dispersion comprising a compound which is free from water solubilising groups of Formula (1):
A--N═N--D                                              Formula (1)
wherein
A and D each independently is an substituted or unsubstituted heterocyclic or carbocyclic group and
at least one of A or D carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached provided that when A1 --N═N-- is a p-fluorosulphonylphenylazo group, that at least one of the positions ortho or meta to the azo group is substituted, that when A1 --N═N-- is a m-fluorosulphonylphenylazo group, that at least 2 of the positions ortho or para to the azo group, or meta to both the fluorosulphonyl group are substituted, that when either A1 or D1 is a phenylene group substituted ortho to the azo group by an --SO2 F group, neither A1 or D1 are substituted at the position para to the azo group by an NO2 group, and also provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, 4-fluorosulphonylnaphth-1-yl, substituted or unsubstituted 1-phenyl-pyrazol-4-yl-5-one or ##STR49## or that one of A or D does not carry an --NCH2 CH(OH)CH2 Cl, --NCOCH2 Cl or --NCH3 CH2 SO2 F substituent and water.
11. A process for colouring polyamide and aromatic polyester textile material or fibre blends thereof which comprises applying to the synthetic textile material a compound, which is free from water solubilising groups, or a mixture of such compounds, of Formula (1):
A--N═N--D                                              Formula (1)
wherein
A and D each independently is a heterocyclic or carbocyclic group, which is unsubstituted or is substituted by one or more substituents selected from the group consisting of cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl,--OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHCOaryl, --NHSO2 alkyl, --NHSO2 aryl, --Salkyl, --Saryl, --SO2 alkyl, --SO2 aryl, --SCN, --NR1 R2 in which R1 and R2 each independently is --H, alkyl, aryl or cycloalkyl, and groups of Formula R19 N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or --NR20 --Z-- or --O--Z-- in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCOR21, --OH or --CN in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or substituted or unsubstituted alkyl, each of the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 being unsubstituted or substituted by one or more of --OH, --CN, --F, --Cl, --Br, --I, --SO2 F, alkoxy, alkenyl, phenyl, phenylSO2 F, aryloxy, aryloxySO2 F, --N(alkyl)2, --OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, --COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO2 F, --OCOphenylNO2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, --OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkyCOalkyl, --COOalkyCOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, --OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, --OalkylCOOalkylCOOalkyl, --OalkylOCOalkyCOalkyl, --COOalkylOCOalkyl or --COOalkylCOOalkyl, ##STR50## in which L is --H or alkyl, and at least one of A or D is substituted by at least one --SO2 F group or is substituted by at least one substituent which is itself substituted by at least one --SO2 F group, except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, substituted or unsubstituted 1-phenyl-pyrazol-4-yl-5-one, 4-fluorosulphonylnaphth-1-yl or ##STR51## or that one of A or D does not carry an --NCH2 CH(OH)CH2 Cl, --NCOCH2 Cl or --NCH2 CH2 SO2 F substituent.
12. A process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound, which is free from water solubilising groups, or a mixture of such compounds, of Formula (1):
A--N═N--D                                              FORMULA (1)
wherein
A and D each independently is a heterocyclic or carbocyclic group, which is unsubstituted or is substituted by one or more substituents selected from the group consisting of cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl, --OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHCOaryl, --NHSO2 alkyl, --NHSO2 aryl, --Salkyl, --Saryl, --SO2 alkyl, --SO2 aryl, --SCN, --NR1 R2 in which R1 and R2 each independently is --H, alkyl, aryl or cycloalkyl, and groups of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkyCOalkyl, alkylNHalkyl or --NR20 --Z-- or --O--Z-- in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCOR21, --OH or --CN in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or substituted or unsubstituted alkyl, each of the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 being unsubstituted or substituted by one or more of --OH, --CN, --F, --Cl, --Br, --I, --SO2 F, alkoxy, alkenyl, phenyl, phenylSO2 F, aryloxy, aryloxySO2 F, --N(alkyl)2, --OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, --COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO2 F, --OCOphenylNO2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, --OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkylOalkyl, --COOalkylOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, --OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, --OalkylCOOalkylCOOalkyl, --OalkylOCOalkylOalkyl, --COOalkylOCOalkyl or --COOalkylCOOalkyl, ##STR52## in which L is --H or alkyl, at least one of A or D being substituted by at least one --SO2 F group or is substituted by at least one substituent which is itself substituted by at least one --SO2 F group, and
at least one of A or D is substituted by at least one ester group or is substituted by at least one substituent which is itself substituted by at least one ester group, provided that one of A or D is not ##STR53##
13. A process for colouring a polyester textile material or fibre blend thereof which comprises applying to the polyester textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1):
A--N═N--D                                              FORMULA (1)
wherein
A and D each independently is a heterocyclic or carbocyclic group, which is unsubstituted or is substituted by one or more substituents selected from the group consisting of cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl,--OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHCOaryl, --NHSO2 alkyl, --NHSO2 aryl, --Salkyl, --Saryl, --SO2 alkyl, --SO2 aryl, --SCN, --NR1 R2 in which R1 and R2 each independently is --H, alkyl, aryl or cycloalkyl, and groups of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or --NR20 --Z-- or --O--Z-- in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCO R21, --OH or --CN in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or substituted or unsubstituted alkyl, each of the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 being unsubstituted or substituted by one or more of --OH, --CN, --F, --Cl, --Br, --I, --SO2 F, alkoxy, alkenyl, phenyl, phenylSO2 F, aryloxy, aryloxySO2 F, --N(alkyl)2, --OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, --COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO2 F, --OCOphenylNO2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, --OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkylOalkyl, --COOalkylOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, --OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, --OalkylCOOalkylCOOalkyl, --OalkylOCOalkylOalkyl, --COOalkylOCOalkyl or --COOalkylCOOalkyl, ##STR54## in which L is --H or alkyl, except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, substituted or unsubstituted 1-phenylpyrazol-4-yl-5one, 4-fluorosulphonylnaphth-1-yl or 4-nitro-2-fluorosulphonylphenyl or that one of A or D does not carry an --NCH2 CH2 SO2 F substitutent.
14. A process according to any one of claims 11 to 13 in which A and D each independently is selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4- and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, phenyl and naphthyl.
15. A process according to any one of claims 11 to 13 in which A and D each independently is selected from thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl, quinolinyl.
16. A process according to any one of claims 11 to 13 in which A and D each independently is selected from thien-2-yl, phenyl, naphth-1-yl, naphth-2-yl, thiazol-2-yl, isothiazol-5-yl, pyrid-4-one-5-yl or quinolinyl.
17. A process according to any one of claims 11 to 13 in which A is thien-2-yl or phenyl and D is phenyl or naphth-1-yl.
18. A process according to any one of claims 11-13 in which the compound of Formula (1) is of Formula (3): ##STR55## wherein R1 and R2 each independently is --H, substituted or unsubstituted C1-6 -alkyl or substituted or unsubstituted aryl;
R3, R4, R5 and R6 each independently is --H , --F, --Cl, --Br, --I, --SO2 F or substituted or unsubstituted C1-6 -alkyl, C1-6 -alkoxy, C1-4 alkanoylamino, --NHSO2 alkyl or phenoxy;
R7, R8 and R9 each independently is --H, C1-6 -alkyl, --NO2, --COOC1-6 -alkyl, --OCOalkyl, --Cl, --F, --Br, --I, --COC1-6 -alkyl, --CN, formyl, protected formyl or --SO2 F provided that at least one of R1 to R9 is substituted by an --SO2 F group or is substituted by a substituent which is itself substituted by at least one --SO2 F group, and provided that R7 and R9 are not both --SO2 F.
19. A process according to any one of claims 11-13 in which the compound of Formula (1) is of Formula (4): ##STR56## wherein R1 and R2 each independently is --H, substituted or unsubstituted C1-6 -alkyl or substituted or unsubstituted aryl;
R3, R4, R5 and R6 each independently is --H, --F, --Cl, --Br, --I, --SO2 F of substituted or unsubstituted C1-6 alkyl, C1-6 -alkoxy, C1-4 -alkanoylamino, --NHSO2 alkyl or phenoxy; and
R10 to R14 each independently is --H, alkoxy, alkyl, --NO2, --SO2 F, --F, --Cl, --Br, --I or --CN; provided that when R10 is SO2 F, R12 is not --NO2 and R11, R13 and R14 are not all --H.
20. A process according to any one of claims 11-13 in which the compound of Formula (1) is of Formula (7): ##STR57## in which R1 and R2 each independently is substituted or unsubstituted C1-6 -alkyl;
R4 is alkyl or a group of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, --NR20 --Z--, --COOZ or --O--Z in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl or a direct link and
R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCOR21 or --OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or alkyl;
R5 is --H, C1-6 -alkoxy or phenoxy;
R10 is --NO2 or --Cl; and
R13 and R14 each independently is --H or --Cl.
21. A process according to any one of claims 11-13 in which the compound of Formula (1) is of Formula (5): ##STR58## wherein R1 and R2 each independently is --H, substituted or unsubstituted C1-6 -alkyl;
R3 is substituted or unsubstituted C1-6 -alkyl or C1-6 -alkoxy;
R4 is substituted or unsubstituted C1-6 -alkyl or C1-6 -alkoxy;
R10 is substituted or unsubstituted C1-6 -alkyl, NO2 or Cl;
R15 to R18 each independently is --H, --C1-6 -alkyl, --C1-6 -alkoxy, --F, --Cl, --Br, --I, --SO2 F, --NO2, --CN or --NR1 R2 ;
R12 is --NO2 or --SO2 F;
R11 is --H; and
R13 and R14 each independently is --H or --Cl.
22. A compound, which is free from water solubilising groups, of Formula (2):
A.sup.1 --N═N--D.sup.1                                 Formula ( 2)
in which
A1 --N═N-- is a substituted or unsubstituted heterocyclic or carbocyclic azo group and D1 is a coupler, each of A1 and D1 independently being selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, 1,2,4- and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyridonyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, phenyl and naphthyl, and at least one of A1 or D1 carries directly at least one --SO2 F group or carries a substituent to which at least one --SO2 F group is attached, provided that when A1 --N═N-- is a p-fluorosulphonylphenylazo group, that at least one of the positions ortho or meta to the azo group is substituted, that when A1 --N═N-- is a m-fluorosulphonylphenylazo group, that at least 2 of the positions ortho or para to the azo group, or meta to both the fluorosulphonyl group are substituted, that when either A1 or D1 is a phenylene group substituted ortho to the azo group by an --SO2 F group, neither A1 or D1 are substituted at the position para to the azo group by an NO2 group, the substituents for A1 and D1 being selected from the group consisting of cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, --COalkyl, --COOalkyl, --OCOalkyl, --COaryl, --COOaryl, --OCOaryl, --NHCOalkyl, --NHSO2 alkyl, --NHSO2 aryl, --Salkyl, --Saryl, --SO2 alkyl, --SO2 aryl, --SCN, --NR1 R2 in which R1 and R2 each independently is --H, alkyl, aryl or cycloalkyl, and groups of Formula R19 --N--Y--X--W in which Y is a direct link or C═O, X is a direct link, alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or --NR20 --Z-- or --O--Z-- in which Z is alkyl, alkenyl, aryl, heterocyclic, alkylOalkyl, alkylNHalkyl or a direct link and R20 is --H, alkyl, aryl or alkylaryl, W is --CO2 R21, --OCOR21, --OH or --CN in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is --H or substituted or unsubstituted alkyl, each of the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 being unsubstituted or substituted by one or more of --OH, --CN, --F, --Cl, --Br, --I, --SO2 F, alkoxy, alkenyl, phenyl, phenylSO2 F, aryloxy, aryloxySO2 F, --N(alkyl)2 --OCOalkyl, --OCOalkylCl, --COOalkyl, --COOalkylOH, --COOalkylCN, --COOalkylCOalkyl, --COOalkylphenyl, --OCOphenyl, --COphenylSO2 F, --OCOphenylNO2, --OCOphenylalkyl, --OCOphenylalkoxy, --COOphenyl, --OCO(fluorosulphonylphenyl), --OalkylCN, --COOalkylOalkyl, --COOalkylOphenyl, --OCOalkylOphenyl, --COOalkylOalkylOalkyl, --OCOalkylCOOalkyl, --OalkylCOOalkyl, --OalkylCOOalkylOalkyl, --OalkylCOOalkylCOOalkyl, --OalkylOCOalkylOalkyl, --COOalkylOCOalkyl or --COOalkylCOOalkyl, ##STR59## in which L is --H or alkyl, provided that A1 is not 3,5-difluorosulphonylthien-2-yl, that one of A1 or D1 is not 4-fluorosulphonylnaphth-1-yl or substituted 4-hydroxynaphth-1-yl, that one of A1 or D1 does not carry a --NCH2 CH2 SO2 F substituent.
US08/676,234 1994-01-19 1994-12-30 Monoazo dyes which are free from water-solubilizing groups and which contain a fluorosulphonyl group and process for colouring polyamides and polyester materials therewith Expired - Lifetime US5739299A (en)

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US20080033153A1 (en) * 2004-07-07 2008-02-07 Riggs-Sauthier Jennifer A Synthesis of Azo Bonded Immunoregulatory Compounds
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US5998592A (en) * 1996-01-26 1999-12-07 Basf Aktiengesellschaft Monoazo dyes containing a fluorosulphonyl group and use thereof
US6048370A (en) * 1996-02-10 2000-04-11 Basf Aktiengesellschaft Monoazo dyes containing a fluorosulphonyl group and use thereof
US5973127A (en) * 1996-06-25 1999-10-26 Basf Aktiengesellschaft Monoazo dyes substituted by haloalkylcarbamate and sulphonylfluoride groups
US7425578B2 (en) 2000-08-29 2008-09-16 Biocon Limited Immunoregulatory compounds and derivatives and methods of treating diseases therewith
US20030191186A1 (en) * 2000-08-29 2003-10-09 Ekwuribe Nnochiri Nkem Immunoregulatory compounds and derivatives and methods of treating diseases therewith
US7119119B2 (en) 2000-08-29 2006-10-10 Biocon Limited Immunoregulatory compounds and derivatives and methods of treating diseases therewith
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CN1886466B (en) * 2003-12-10 2011-01-26 克莱里安特财务(Bvi)有限公司 Disperse dyes
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CN103319380B (en) * 2013-05-28 2015-11-25 江苏之江化工有限公司 A kind of dyestuff containing fluorine element
CN103319380A (en) * 2013-05-28 2013-09-25 江苏之江化工有限公司 Fluorine-containing dye
CN103602095A (en) * 2013-09-10 2014-02-26 江苏亚邦染料股份有限公司 Monoazo-type disperse dyes, preparation method thereof and applications thereof
CN103602095B (en) * 2013-09-10 2016-04-20 江苏亚邦染料股份有限公司 One class Monoazo type dispersed dye, preparation method and application
CN105542508A (en) * 2016-01-20 2016-05-04 俞杏英 Disperse dye monomeric compound as well as preparation method and application of disperse dye monomeric compound
CN106280535A (en) * 2016-08-08 2017-01-04 绍兴文理学院 A kind of high washing fastness disperse dyes and preparation method and application
CN106977975A (en) * 2017-04-24 2017-07-25 苏州科法曼化学有限公司 Azo dispersion dyes compound and its synthetic method and tint applications
CN106977975B (en) * 2017-04-24 2019-09-24 苏州科法曼化学有限公司 Azo dispersion dyes compound and its synthetic method and tint applications
CN110776439A (en) * 2019-11-06 2020-02-11 蓬莱嘉信染料化工股份有限公司 Azo compound, preparation method and application thereof, dye composition, dye, preparation method and application thereof
CN110776439B (en) * 2019-11-06 2022-11-01 蓬莱嘉信染料化工股份有限公司 Azo compound, preparation method and application thereof, dye composition, dye, preparation method and application thereof

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KR970700732A (en) 1997-02-12
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ZA95311B (en) 1995-11-28
DE69427543D1 (en) 2001-07-26
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EP0740690A1 (en) 1996-11-06
GB9400972D0 (en) 1994-03-16
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TW348194B (en) 1998-12-21
DE69427543T2 (en) 2002-06-20

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